TW201435493A - Photosensitive resin composition, protective film or insulation film obtained by heat curing said composition, touch panel using said film, and production method for said touch panel - Google Patents

Abstract

The purpose of the present invention is to provide an alkali developable photosensitive resin composition which exhibits excellent coating-liquid storage stability and no reduction in adhesive properties during storage, and with which a cured film exhibiting a high hardness, and excellent transparency, moist-heat resistance, synthetic sweat resistance, adhesive properties, chemical resistance, and vacuum resistance, can be produced. Accordingly, provided is a photosensitive resin composition which includes an acrylic resin (A), a radically polymerizable compound (B), a photopolymerization initiator (C), a metal chelate compound (D), and a solvent (E), said acrylic resin (A) having a structure derived from a maleimide having a specific structure.

Description

Photosensitive resin composition, protective film or insulating film obtained by heating same, touch panel using the same, and manufacturing method thereof

The present invention relates to a photosensitive resin composition, a protective film or an insulating film obtained by thermally curing the same, a touch panel using the same, and a method for producing the same.

In recent years, with the popularity of smart phones or tablet terminals, electrostatic capacitive touch panels have attracted attention. The sensor substrate of the capacitive touch panel is generally provided with patterned wiring of ITO (Indium Tin Oxide) or metal (silver, molybdenum or aluminum) on the glass, and has insulation at the intersection of the wiring. The structure of the film and the protective film for protecting ITO and metal. In many cases, the protective film is formed of high-hardness inorganic SiO ₂ or SiN _x or a photosensitive transparent material (Patent Document 1), and the insulating film is formed of a photosensitive transparent material. However, there will be an inorganic material-based SiN _x or SiO ₂ by CVD (Chemical Vapor Deposition) film is formed at high temperature, and to the use of the resist pattern and the number of processing programs and the like to increase the manufacturing cost becomes high. Furthermore, there is a lack of heat and humidity resistance, and the metal wiring of the substrate is corroded, etc., and a highly reliable touch panel cannot be obtained.

Regarding the photosensitive transparent material, although it is expected that the cost is reduced by the reduction in the number of programs, the hardness is insufficient, and the inorganic material is In the same manner, the material has low heat and humidity resistance, and in the reliability test, there is a problem that the metal wiring of the substrate is corroded or the like. Further, similarly in the reliability test, it is also required to suppress corrosion of the metal wiring of the substrate due to the intrusion of the artificial sweat solution.

The cured film obtained from the photosensitive transparent material is exposed to various acidic or alkaline liquids such as an etching liquid for processing metal wiring of ITO or a substrate, and if the cured film has low chemical resistance, the cured film is The interface of the metal wiring or the substrate of the substrate may be peeled off or erected, which may cause disconnection of the ITO or the like. In addition, since the cured film obtained from the photosensitive transparent material is exposed to a high vacuum state during film formation of ITO, if the resistance to vacuum is low, the cured film is deteriorated by the exhaust gas from the cured film, and the like. The reason for the decrease in the adhesion.

In addition, when the coating liquid of the photosensitive transparent material is stored at room temperature, there is a problem that the material is deteriorated during storage and the adhesion to the substrate is lowered. Therefore, high hardness is strongly required, and transparency, moist heat resistance, artificial sweat resistance, adhesion, chemical resistance, and vacuum resistance are excellent, and pattern processing can be performed in an alkaline developing solution, and the storage stability of the coating liquid is good. A photosensitive transparent material that does not reduce the adhesion during storage.

In order to improve the problem as described above, a photosensitive transparent material containing a polyfunctional epoxy compound (Patent Document 3), a photosensitive transparent material containing a metal chelate compound such as a zirconium compound (Patent Document 4), and a device have been developed. Photosensitive transparent material of acrylic resin derived from the structure of maleimide (Patent Document 5) or contains three A photosensitive transparent material of a compound (Patent Document 6).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2007-279819

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2006-30809

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2010-24434

[Patent Document 4] International Publication No. 2011/129210

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2003-192746

[Patent Document 6] Japanese Patent Laid-Open Publication No. 2010-128275

However, the present state of the art is to satisfy the high hardness of the obtained cured film, and is excellent in transparency, moist heat resistance, artificial sweat resistance, adhesion, chemical resistance, and vacuum resistance, and can be patterned in an alkali developer, and the coating liquid It is still completely unknown that all the photosensitive transparent materials which have good storage stability and are not deteriorated in storage during storage are not known.

Therefore, an object of the present invention is to provide a photosensitive resin composition capable of alkaline development, which has high hardness at the same time, and is excellent in transparency, moist heat resistance, artificial sweat resistance, adhesion, chemical resistance and vacuum resistance. The cured film is excellent in storage stability of the coating liquid and does not deteriorate the adhesion during storage.

The present invention provides a photosensitive resin composition comprising (A) an acrylic resin, (B) a radical polymerizable compound, (C) a photopolymerization initiator, (D) a metal chelate compound, and (E) a solvent. Photosensitive resin The composition, and the above (A) acrylic resin has a structure having a specific structure derived from maleimide.

According to the photosensitive resin composition of the present invention, a cured film having high hardness and excellent transparency, moist heat resistance, artificial sweat resistance, adhesion, chemical resistance, and vacuum resistance can be obtained. Moreover, according to the photosensitive resin composition of the present invention, it is possible to prepare a coating liquid which is excellent in storage stability and which does not deteriorate in adhesion during storage.

a‧‧‧Top surface after transparent electrode formation

b‧‧‧Top surface after the formation of the insulating film

c‧‧‧Top surface diagram after metal wiring is formed

1‧‧‧ glass substrate

2‧‧‧Transparent electrode

3‧‧‧Transparent insulating film

4‧‧‧Wiring electrode

5‧‧‧Transparent protective film

Fig. 1 is a schematic top view showing a manufacturing process of a touch panel member.

Fig. 2 is a schematic cross-sectional view showing a touch panel member.

[Formation of the Invention]

The photosensitive resin composition of the present invention is characterized by comprising (A) an acrylic resin, (B) a radical polymerizable compound, (C) a photopolymerization initiator, (D) a metal chelate compound, and (E) a solvent, and The above (A) acrylic resin has a structure derived from maleimide represented by the general formula (1).

(X represents a direct bond, an alkyl chain having a carbon number of 1 to 10, a stretched alkyl chain having a carbon number of 4 to 10, or an extended aryl chain having a carbon number of 6 to 15, and R ¹ represents hydrogen and a carbon number of 1~ 10 alkyl, 4 to 10 cycloalkyl, 2 to 7 alkenyl, 6 to 15 aryl, 1 to 6 alkoxy, 2 to 7 carbon An oxy group, an ester group having 2 to 7 carbon atoms, a hydroxyl group, a carboxyl group, an amine group or a nitro group).

The photosensitive resin composition of the present invention contains (A) an acrylic resin. Since the (A) acrylic resin has a structure derived from maleimide represented by the formula (1), the hardness, chemical resistance, and vacuum resistance of the obtained cured film can be improved without impairing the storage stability of the coating liquid. , heat and humidity resistance, artificial sweat resistance and heat resistance. When the (A) acrylic resin does not have such a structure, the storage stability of the coating liquid is poor, the reaction proceeds during storage of the coating liquid, and the photosensitive resin composition is deteriorated, and chemical resistance, adhesion, and the like are lowered. Therefore, it is speculated that this structure contributes to stabilization and suppresses the progress of the reaction. Further, it is presumed that (A) the acrylic resin has such a structure, promotes the reaction at the time of thermosetting, increases the crosslinking density, and improves the hardness, vacuum resistance, moist heat resistance, and artificial sweat resistance of the obtained cured film. Again. It is considered that this structure acts as a site capable of coordinating on the surface of the substrate of the substrate, thereby enhancing the chemical resistance of the obtained cured film. The (A) acrylic resin preferably has an aromatic cyclic skeleton or an aliphatic cyclic skeleton in this structure. It is considered that the chemical resistance, vacuum resistance, moist heat resistance, artificial sweat resistance and heat resistance of the obtained cured film are further enhanced by the hydrophobicity or chemical stability of the aromatic cyclic skeleton or the aliphatic cyclic skeleton. .

In the structure derived from maleimide represented by the formula (1) of the (A) acrylic resin, X is preferably a direct bond, an alkyl group having a carbon number of 1 to 6, and a carbon number of 4~. A stretched alkyl chain of 7 or an extended aryl chain of 6 to 10 carbon atoms. When X is a direct bond, R ^{1 is} preferably hydrogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, and an aromatic group having 6 to 15 carbon atoms. The ester group or the hydroxyl group having 2 to 7 carbon atoms is more preferably hydrogen, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or a carbon number of 6~ An aryl group of 10, an ester group having 2 to 5 carbon atoms or a hydroxyl group. When X is an alkylene chain, R ^{1 is} preferably an aryl group having 6 to 15 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkenyloxy group having 2 to 7 carbon atoms, and an ester having 2 to 7 carbon atoms. a group, a hydroxyl group or a carboxyl group, more preferably an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkenyloxy group having 2 to 5 carbon atoms, an ester group having 2 to 5 carbon atoms, a hydroxyl group or a carboxyl group. . When X is an aryl chain, R ^{1 is} preferably an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an ester group having 2 to 7 carbon atoms. a hydroxyl group, a carboxyl group, an amine group or a nitro group, more preferably an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an ester group having 2 to 5 carbon atoms. , hydroxyl, carboxyl, amine or nitro.

The above alkyl chain, cycloalkyl chain, aryl chain, alkyl group, cycloalkyl group, alkenyl group, aryl group, alkoxy group, alkenyloxy group, ester group and amine group may be unsubstituted Any of the things or substitutes.

(A) The content ratio of the structure derived from the maleimide represented by the formula (1) in the acrylic resin, hardness, chemical resistance, vacuum resistance, moist heat resistance, artificial sweat resistance, heat resistance from the cured film The viewpoint of improving the storage stability of the coating liquid is preferably from 5 to 80 mol%, more preferably from 7 to 70 mol%, still more preferably from 10 to 60 mol%.

Since the (A) acrylic resin has a carboxyl group, it is possible to process the system with an alkali developer. As the acid value of (A) acrylic resin, It is preferably 40 to 200 mgKOH/g, more preferably 50 to 180 mgKOH/g, still more preferably 70 to 140 mgKOH/g. The acid value herein means the weight of KOH which reacts with an acidic group in 1 g of the resin, and the unit is mgKOH/g. The acid number in the resin can be determined from the value of the acid value. When the acid value is in the above range, the residue of the photosensitive resin composition after development of the alkaline developing solution can be suppressed, and the film of the exposed portion can be suppressed from being thinned and a good pattern can be formed.

Since (A) the acrylic resin has an ethylenically unsaturated double bond group, while promoting UV hardening at the time of exposure and improving sensitivity, the crosslinking density after heat hardening is increased and the hardness of the cured film is increased. The double bond equivalent of the (A) acrylic resin is preferably from 150 to 10,000 g/mol, more preferably from 200 to 5,000 g/mol, still more preferably from 250 to 2,000 g/mol. The double bond equivalent here means the weight of the resin per 1 mol of the unsaturated group, and the unit is g/mol. The double bond equivalent system can be calculated by measuring the iodine value. Since the double bond equivalent is in the above range, the hardness and crack resistance of the cured film can be combined at a high level.

The weight average molecular weight (Mw) of the (A) acrylic resin is preferably 2,000 to 100,000, more preferably 5,000 to 40,000, in terms of polystyrene measured by gel permeation chromatography (GPC). When the weight average molecular weight (Mw) is less than 2,000, the tack free performance is poor, and the moisture resistance of the coating film after exposure is poor, and the film is thinned during development, and the resolution is deteriorated. On the other hand, when the weight average molecular weight (Mw) exceeds 100,000, the developability is remarkably deteriorated, and the storage stability of the coating liquid is also deteriorated.

As the (A) acrylic resin, a maleic imine or a maleimine derivative, a (meth)acrylic acid having a carboxyl group or an acid anhydride group is preferred. The compound and other (meth) acrylate are free radical copolymerized. Examples of the radical polymerization initiator used for the radical copolymerization include, for example, 2,2'-azobis(isobutyronitrile) and 2,2'-azobis(2,4-dimethylvaleronitrile). An azo compound or a lauroyl peroxide, dibutyl butyl peroxide, bis(4-tert-butylcyclohexane-1-yl)peroxydicarbonate, 2-ethylperoxy An organic peroxide such as a tertiary butyl ester, methyl ethyl ketone peroxide, benzoyl saccharide or cumene hydroperoxide.

The conditions of the radical copolymerization can be suitably set, but it is preferred to, for example, completely replace the nitrogen in the reaction vessel by bubbling or degassing under reduced pressure, and then add a copolymerization component to the solvent and initiate polymerization by radical polymerization. The reaction is carried out at 60 to 110 ° C for 30 to 500 minutes. When a (meth)acrylic acid compound having an acid anhydride group is used as a copolymerization component, it is preferred to add a theoretical amount of water, and the reaction is allowed to proceed at 30 to 60 ° C for 30 to 60 minutes. Further, a chain transfer agent such as a thiol compound may be used as needed.

Examples of the maleic imine or the maleimide derivative include maleimide, N-methyl maleimide, N-ethyl maleimide, and N-n-propyl group. Maleimide, N-isopropylmaleimide, N-n-butylmaleimide, N-t-butylmaleimide, N-n-hexylmaleimide, N-dido-maleimide, N-cyclopentylmaleimide, N-cyclohexylmaleimide, N-(2,4-dimethylcyclohexyl)maleimide , N-vinyl maleimide, N-(meth)acrylic acid maleimide, N-methoxymethyl maleimide, N-(2-ethoxyethyl) horse醯imine, N-(4-butoxyethyl)maleimide, N-[(meth)acryloxymethyl]maleimide, N-[2-(methyl Acryloxyethyl ]Maleimine, N-[3-(methyl)acryloxypropyl]maleimide, N-methoxycarbonylmaleimide, N-(3-methoxycarbonyl Propyl) maleimide, N-(2-hydroxyethyl)maleimide, N-(4-hydroxy-n-butyl)maleimide, N-(2-carboxyethyl) Maleidin, N-(3-carboxypropyl)maleimide, N-(5-carboxypentyl)maleimide, N-phenylmaleimide, N-(4 -methylphenyl)maleimide, N-(3-methylphenyl)maleimide, N-(2-methylphenyl)maleimide, N-(2,6 -dimethylphenyl)maleimide, N-(2,6-diethylphenyl)maleimide, N-(4-styryl)maleimide, N-( 4-methoxyphenyl)maleimide, N-(3-methoxyphenyl)maleimide, N-(2-methoxyphenyl)maleimide, N- (4-methoxycarbonylphenyl)maleimide, N-(4-hydroxyphenyl)maleimide, N-(3-hydroxyphenyl)maleimide, N-(2 -hydroxyphenyl)maleimide, N-(4-carboxyphenyl)maleimide, N-(1-naphthyl)maleimide, N-benzylmaleimide or N-(2-phenylethyl)maleimide, but hardened from From the viewpoints of improvement in chemical resistance, vacuum resistance, moist heat resistance, artificial sweat resistance and heat resistance, N-cyclopentylmaleimide, N-cyclohexylmaleimide, N- are preferred. (2,4-Dimethylcyclohexyl)maleimide, N-phenylmaleimide, N-(4-methylphenyl)maleimide, N-(3-methyl Phenyl)maleimide, N-(2-methylphenyl)maleimide, N-(2,6-dimethylphenyl)maleimide, N-(2,6 -diethylphenyl)maleimide, N-(4-styryl)maleimide, N-(4-methoxyphenyl)maleimide, N-(3- Methoxyphenyl)maleimide, N-(2-methoxyphenyl)maleimide, N-(4-methoxycarbonylphenyl)maleimide, N-( 4-hydroxyphenyl)maleimide, N-(3-hydroxyphenyl)maleimide, N-(2-hydroxyphenyl)ma 醯iimine, N-(4-carboxyphenyl)maleimide, N-(1-naphthyl)maleimide, N-benzylmaleimide or N-(2-benzene Base ethyl) maleimide.

Examples of the (meth)acrylic compound having a carboxyl group or an acid anhydride group include (meth)acrylic acid, (meth)acrylic anhydride, itaconic acid, itaconic anhydride, and succinic acid mono(2-acryloxyloxyethyl). Ester), mono(2-propenyloxyethyl) phthalate or mono(2-propenyloxyethyl) tetrahydrophthalate.

Examples of the (meth) acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, and (methyl). Cyclopentyl acrylate, cyclohexyl (meth) acrylate, cyclohexene (meth) acrylate, (4-methoxy) cyclohexyl (meth) acrylate, (2- isopropyl) Oxycarbonyl)ethyl ester, (2-cyclopentyloxycarbonyl)ethyl (meth)acrylate, (2-cyclohexyloxycarbonyl)ethyl (meth)acrylate, (meth)acrylic acid (2-ring) Hexenyloxycarbonyl)ethyl ester, [2-(4-methoxycyclohexyl)oxycarbonyl]ethyl (meth)acrylate, norbornyl (meth)acrylate, isobornyl (meth)acrylate , tricyclodecyl (meth)acrylate, tetracyclodecyl (meth)acrylate, dicyclopentenyl (meth)acrylate, adamantyl (meth)acrylate, (meth)acrylic acid (adamantyl) Methyl ester or (1-methyl) adamantyl (meth)acrylate.

As another copolymerization component, an aromatic vinyl compound such as styrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene or α-methylstyrene can be used, but the obtained It is preferable to use styrene in view of improvement in chemical resistance, vacuum resistance, moist heat resistance, artificial sweat resistance, and heat resistance of the cured film.

As the (A) acrylic resin having an ethylenically unsaturated double bond group, it is preferred to further carry out an epoxy group-containing unsaturated compound having an ethylenically unsaturated double bond group for radical copolymerization of maleic imine or A maleidene derivative, a (meth)acrylic compound having a carboxyl group or an acid anhydride group, and another (meth)acrylate are obtained by a ring-opening addition reaction. The catalyst for the ring-opening addition reaction of the epoxy group-containing unsaturated compound may, for example, be triethylamine, dimethylaniline, tetramethylethylenediamine or 2,4,6-gin ( An amine-based catalyst such as dimethylaminomethyl)phenol, dimethylbenzylamine or tri-n-octyldecylamine; tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium fluoride, etc. An alkyl halide such as a quaternary ammonium salt or tetramethyl urea, an alkyl hydrazine such as tetramethyl hydrazine, tin (II) bis(2-ethylhexanoate) or di-n-butyltin dilaurate (IV). Titanium catalyst such as tin-based catalyst, titanium (2-ethylhexanoic acid) titanium (IV), phosphorus-based catalyst such as triphenylphosphine or triphenylphosphine oxide, and acetylacetate a chromium-based catalyst such as chromium (III), chromium (III) chloride, chromium (III) octenate or chromium (III) naphthenate or cobalt-based catalyst such as cobalt (II) octylate Wait.

Examples of the epoxy group-containing unsaturated compound include glycidyl (meth)acrylate, (α-ethyl)epoxypropyl (meth)acrylate, and (meth)acrylic acid (α-n-propyl). Glycidylpropyl ester, (α-n-butyl) g-propyl (meth)acrylate, (3,4-epoxy) n-butyl (meth)acrylate, (meth)acrylic acid (3, 4-epoxy)heptyl ester, (meth)acrylic acid (α-ethyl-6,7-epoxy)heptyl ester, allyl epoxypropyl ether, vinyl epoxypropyl ether, 2- Vinylbenzylepoxypropyl ether, 3-vinylbenzylepoxypropyl ether, 4-vinylbenzylepoxypropyl ether, α-methyl-2-vinylbenzylepoxypropyl ether , α-methyl-3-vinylbenzyl epoxypropyl ether, α-methyl-4- Vinyl benzyl epoxypropyl ether, 2,3-bis(glycidoxymethyl)styrene, 2,4-bis(glycidoxymethyl)styrene, 2,5-bis ( Glycidoxymethyl)styrene, 2,6-bis(glycidoxymethyl)styrene, 2,3,4-glycol (glycidoxymethyl)styrene, 2,3 , 5-glycol (glycidoxymethyl)styrene, 2,3,6-glycol (glycidoxymethyl)styrene, 3,4,5-paran (glycidoxymethyl) Styrene or 2,4,6-gin (glycidoxymethylstyrene).

In the photosensitive resin composition of the present invention, the content of the (A) acrylic resin is 100 parts by weight based on the total of the (A) acrylic resin and the (B) radical polymerizable compound, and the hardness and resistance of the cured film are From the viewpoints of improvement in chemical properties, vacuum resistance, moist heat resistance, artificial sweat resistance, heat resistance, and storage stability of the coating liquid, it is preferably 10 to 80 parts by weight, more preferably 20 to 70 parts by weight, further Good is 30~60 parts by weight.

The photosensitive resin composition of the present invention may further contain (A) an acrylic resin other than the acrylic resin. As such an acrylic resin, the acid value, the double bond equivalent weight, and the weight average molecular weight (Mw) are preferably in the same range as the (A) acrylic resin.

The acrylic resin other than the (A) acrylic resin is preferably a radical copolymerization of a (meth)acrylic compound having a carboxyl group or an acid anhydride group and another (meth)acrylate. A radical polymerization initiator for radical copolymerization, a condition of radical copolymerization, a (meth)acrylic acid compound having a carboxyl group or an acid anhydride group, a (meth) acrylate, and other copolymerized aromatic vinyl The base compound may be the same as the case of obtaining the (A) acrylic resin.

Ethylene unsaturated as (A) acrylic resin And a double bond-based acrylic resin, preferably an epoxy group-containing unsaturated compound having an ethylenically unsaturated double bond group, a (meth)acrylic compound having a carboxyl group or an acid anhydride group for radical copolymerization, and the like The (meth) acrylate is obtained by a ring-opening addition reaction. The catalyst for the ring-opening addition reaction of the epoxy group-containing unsaturated compound and the epoxy group-containing unsaturated compound can be obtained by obtaining the (A) acrylic resin having an ethylenically unsaturated double bond group. the same.

In the photosensitive resin composition of the present invention, the content of the acrylic resin other than the acrylic resin (A) is (A) an acrylic resin, (B) a radically polymerizable compound, and (A) an acrylic resin other than the acrylic resin. When the total amount is 100 parts by weight, it is preferably 1 to 20 parts by weight, more preferably 1 to 10 parts by weight.

The photosensitive resin composition of the present invention contains (B) a radically polymerizable compound. The (B) radically polymerizable compound is a compound having a plurality of ethylenically unsaturated double bond groups in the molecule, but is preferably a radical polymerizable having a (meth)acrylic group which is easily subjected to radical polymerization. Compound. By the light irradiation, the (B) radical polymerizable compound is polymerized by the radical generated by the (C) photopolymerization initiator described later, and the exposed portion of the photosensitive resin composition is insolubilized in the alkaline aqueous solution. Form a pattern. The double bond equivalent of the (B) radical polymerizable compound is preferably from 80 to 400 g/mol from the viewpoint of the sensitivity at the time of exposure and the hardness of the cured film.

Examples of the (B) radical polymerizable compound include diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and tetraethylene glycol di(meth)acrylate. Propylene glycol di(meth)acrylate, Trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, trimethylolpropane tetra (Meth) acrylate, 1,3-butylene glycol di(meth) acrylate, neopentyl glycol di(meth) acrylate, 1,4-butanediol di(meth) acrylate, 1 ,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-nonanediol di(meth)acrylate, dimethylol tricyclo Decane di(meth)acrylate, ethoxylated glycerol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ethoxylated pentaerythritol tetra(methyl) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, pentaerythritol IX (methyl) Acrylate, pentaerythritol deca (meth) acrylate, pentaerythritol eleven (meth) acrylate, pentaerythritol dodeca (meth) acrylate, ethoxylated bisphenol A Sensitivity from (meth) acrylate, ginseng ((meth) propylene oxyethyl) isocyanuric acid or bis((meth) propylene methoxyethyl) isocyanuric acid From the viewpoint of improving the hardness of the cured film, it is preferably trimethylolpropane tri(meth)acrylate, trimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate. , pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, Reference to ((meth)acryloxyethyl)isocyanuric acid or bis((meth)acryloxyethyl)isocyanuric acid.

The content of the (B) radically polymerizable compound in the photosensitive resin composition of the present invention is as free as (A) acrylic resin and (B) When the total amount of the base polymerizable compound is 100 parts by weight, it is usually 20 to 90 parts by weight, and from the viewpoint of improving the hardness and chemical resistance of the cured film, it is preferably 30 to 80 parts by weight, more preferably 40 to 70 parts by weight. Parts by weight.

The photosensitive resin composition of the present invention contains (C) a photopolymerization initiator. As the (C) photopolymerization initiator, it is preferred to decompose and/or react by light (including ultraviolet rays or electron beams) to cause radical generation.

The (C) photopolymerization initiator may, for example, be 2-methyl-1-[4-(methylthio)phenyl]-2- Polinyl propan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4- Phenylphenyl)-butan-1-one, 2-benzyl-2-dimethylamino-1-(4- Phenylphenyl)-butan-1-one or 3,6-bis(2-methyl-2- α-Aminoalkylphenone compound such as phenylpropanyl)-9-octyl-9H-carbazole, 2,4,6-trimethylbenzylidene-diphenylphosphine oxide, double (2,4,6-trimethylbenzylidene)-phenylphosphine oxide or bis(2,6-dimethoxybenzylidene)-(2,4,4-trimethylpentyl) a mercaptophosphine oxide compound such as a phosphine oxide, 1-phenylpropene-1,2-dione-2-(O-ethoxycarbonyl)anthracene, 1-[4-(phenylthio)benzene 1, octane-1,2-dione-2-(O-benzylidene) fluorene, 1-phenylbutyr-1,2-dione-2-(O-methoxycarbonyl) hydrazine, 1, 3-diphenylpropane-1,2,3-trione-2-(O-ethoxycarbonyl)anthracene, 1-[9-ethyl-6-(2-methylbenzhydryl)-9H -oxazol-3-yl]ethanone-1-(O-ethylindenyl)purine or 1-[9-ethyl-6-[2-methyl-4-[1-(2,2-di) Methyl-1,3-dioxolan-4-yl)methoxy]benzhydryl]-9H-indazol-3-yl]ethanone-1-(O-ethenyl)anthracene An oxime ester compound, diphenyl ketone, 4,4'-bis(dimethylamino)diphenyl ketone, 4,4'-bis(diethylamino)diphenyl ketone, 4-phenyl bis Phenyl ketone, 4,4-dichlorodiphenyl ketone, 4-hydroxydiphenyl ketone, alkylated diphenyl ketone, 3,3',4,4'-fluorene (t-butylperoxycarbonyl) Diphenyl ketone, 4-methyl a diphenyl ketone derivative such as phenyl ketone, dibenzyl ketone or fluorenone, ethyl 4-dimethylaminobenzoate or (2-ethylhexyl) 4-dimethylaminobenzoate , 4-diethylaminobenzoic acid ethyl ester or benzoate compound such as 2-benzylidenebenzoic acid methyl ester, 2,2-diethoxyacetophenone, 2,3-diethyl Oxyacetophenone, 4-tert-butyldichloroacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,2-dimethoxy-1,2- Diphenylethan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2 -hydroxy-2-methylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methylpropan-1-one, 2-hydroxy-1- [4-[4-(2-Hydroxy-2-methylpropenyl)benzyl]phenyl]-2-methylpropan-1-one, benzal acetophenone or 4-azidobenzylidene An aromatic ketone compound such as acetophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone or thioxanthone compound such as 2,4-dichlorothioxanthone, benzyl methoxyethyl acetal, benzoin, benzoin methyl ether, benzene Even marriage Ether, benzoin isopropyl ether, benzoin isobutyl ether, 4-benzylidene-N,N-dimethyl-N-[2-(1-oxo-2-propenyloxy) Ethyl]benzylammonium bromide, (4-benzylidenebenzyl)trimethylammonium chloride, 2-hydroxy-3-(4-benzylidenephenoxy)-N,N,N- Trimethyl-1-propylammonium chloride monohydrate, 2-hydroxy-3-(3,4-dimethyl-9-oxo-9H-thioxan-2-yloxy)-N,N, N-trimethyl-1-propylammonium chloride, naphthalenesulfonium chloride, quinoline sulfonium chloride, 2,2'-bis(2-chlorophenyl)-4,5,4',5'-tetraphenyl Base-1,2-bisimidazole, 10-n-butyl-2-chloroacridone, N-phenylthioacridone, 1,7-bis(acridin-9-yl)-hexane, hydrazine, 2-ethyl hydrazine, 2-tert-butyl hydrazine, 2-amino hydrazine, β-chloropurine, fluorenone, benzofluorenone, methylene fluorenone, 9,10-phenanthrenequinone, Camphorquinone, dibenzocycloheptanone, methylphenylglyoxylate, η5-cyclopentadienyl-η6-isopropylphenyl-iron (1+)-hexafluorophosphate (1-), 4 -benzimidyl-4'-methyl-diphenyl sulfide, diphenyl sulfide derivative, bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6- Difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium, 2,6-bis(4-azidobenzylidene)cyclohexane 2,6-bis(4-azidobenzylidene)-4-methylcyclohexanone, benzothiazole disulfide, triphenylphosphine, carbon tetrabromide, tribromophenylphosphonium or benzoyl peroxide The combination of a photoreductive pigment such as a fluorenyl group or a ruthenium or methylene blue with a reducing agent such as ascorbic acid or triethanolamine is preferably an α-aminoalkylbenzene from the viewpoint of improving the hardness of the cured film. A ketone compound, a mercaptophosphine oxide compound, an oxime ester compound, a diphenyl ketone compound having an amine group, or a benzoate compound having an amine group.

The diphenyl ketone compound having an amine group may, for example, be 4,4'-bis(dimethylamino)diphenyl ketone or 4,4'-bis(diethylamino)diphenyl ketone. .

The benzoate compound having an amine group may, for example, be ethyl 4-dimethylaminobenzoate, (2-ethylhexyl) 4-dimethylaminobenzoate or 4-diethyl. Ethyl benzoate.

In the photosensitive resin composition of the present invention, the content of the (C) photopolymerization initiator is preferably 0.1% in terms of 100 parts by weight of the total of the (A) acrylic resin and the (B) radical polymerizable compound. 20 parts by weight, more preferably 1 to 10 parts by weight. When the content of the (C) photopolymerization initiator is less than 0.1 part by weight, UV curing does not sufficiently proceed, and film thinning occurs during development, which causes a decrease in resolution. On the other hand, when the amount is more than 20 parts by weight, the UV curing proceeds excessively, which causes the residue after development, and the residual photopolymerization initiator is eluted. However, there is a case where the chemical resistance of the cured film is lowered.

The photosensitive resin composition of the present invention contains (D) a metal chelate compound. By containing the (D) metal chelate compound, the obtained cured film can be improved in chemical resistance, vacuum resistance, moist heat resistance, and artificial sweat resistance. It is presumed that this metal chelate compound is incorporated as part of the three-dimensional network structure formed by thermal hardening by the reaction of heat with a resin or the like. In other words, it is considered that the atoms having a relatively large size are incorporated into the cured film, the film density of the cured film is increased, and the permeability of the liquid chemical solution is lowered, so that the obtained cured film is resistant to chemicals and vacuum. Resistance, moist heat resistance and artificial sweat resistance are improved.

The (D) metal chelate compound may, for example, be a titanium chelate compound, a zirconium chelate compound, an aluminum chelate compound, a magnesium chelate compound, a zinc chelate compound, an indium chelate compound, a tin chelate compound or a copper chelate compound. Compound.

From the viewpoint of the adhesion of the cured film, a titanium chelate compound, a zirconium chelate compound, an aluminum chelate compound or a magnesium chelate compound is preferable, from the viewpoints of heat resistance and artificial sweat resistance of the cured film, More preferably, it is a zirconium chelate compound.

These metal chelating compounds can be easily obtained by reacting a chelating agent with a metal alkoxide. The chelating agent may, for example, be β-diketone such as acetamidineacetone, benzamidineacetone or benzoylmethane or acetonitrile ethyl acetate or benzhydrylacetate. Ketoesters.

The (D) metal chelating compound may, for example, be cerium (ethionylacetate) titanium (IV) or diisopropoxy bis(ethyl acetonitrile acetate) titanium. (IV), diisopropoxy bis(ethyl decyl acetonide) titanium (IV), di-n-octyloxy bis(octylene glycol) titanium (IV), diisopropoxy bis (triethanol amide) Titanium chelate compound such as titanium (IV), dihydroxybis(2-hydroxypropionate) titanium (IV) or dihydroxybis(2-hydroxypropionate) titanium (IV) ammonium salt, hydrazine Root) zirconium (IV), di-n-butoxy bis(ethylacetamidine acetate) zirconium (IV), tri-n-butoxy mono(ethenylacetate) zirconium (IV) or tri-n-butoxy Single (stearate) zirconium chelate compound such as zirconium (IV), ginseng (acetonitrile acetonide) aluminum (III), ginseng (ethyl acetoacetate) aluminum (III), mono (ethyl acetonide) Root) bis(ethylacetamidine acetate) aluminum (III), diisopropoxy mono(ethylacetamidine acetate) aluminum (III) or Plenact (registered trademark) AL-M (diisopropoxy) Single (9-octadecylacetate) aluminum (III), Kasei Precision Chemical Co., Ltd., aluminum chelate compound, bis(ethylmercaptoacetate) magnesium (II), bis (ethyl) Magnesium chelate of acetamidine acetate) magnesium (II), isopropoxy mono(ethylmercaptoacetate) magnesium (II) or isopropoxy mono(ethylacetamidine acetate) magnesium (II) Compound, bis(ethylmercaptoacetate) zinc ( II) either a zinc chelate compound such as bis(ethylacetamidine acetate) zinc (II), bis(ethylmercaptoacetate) indium (III) or bis(ethylacetamidine acetate) indium (III) a tin chelate compound such as an indium chelate compound, bis(ethenylacetonate) tin (II) or bis(ethylacetamidine acetate) tin (II) or bis(ethenylacetate) A copper chelate compound such as copper (II) or bis(ethylacetamidine acetate) copper (II).

The (D) metal chelate compound is preferably a compound represented by the formula (2).

(M represents titanium, zirconium, aluminum or magnesium, R ² represents hydrogen, alkyl having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms or an aryl group having 6 to 15, R ³ and R ⁴ each Independently represents hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a hydroxyl group, and n is 0 to 4 The integer).

R ^{2 is} preferably hydrogen, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms or an aryl group having 6 to 10 carbon atoms, and R ³ and R ⁴ are each independently hydrogen and carbon number. An alkyl group of 1 to 18, a cycloalkyl group having 4 to 7 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydroxyl group. The above alkyl group, cycloalkyl group, aryl group and alkoxy group may also be either an unsubstituted or substituted one. The M system is preferably zirconium as described above.

The compound represented by the formula (2) may, for example, be cerium (ethylidene acetonide) titanium (IV), diisopropoxy bis(ethyl acetamidine acetate) titanium (IV) or diiso. a titanium chelate compound such as propoxy bis(ethenylacetonate) titanium (IV), zirconium (IV) ruthenium (ethenylacetonate), zirconium di-n-butoxy bis(ethylacetate acetate) (IV) or zirconium chelate compound of zirconium (IV) such as tri-n-butoxy mono(ethenylacetate), acetyl (III), ginseng (ethyl acetoacetate) Aluminum (III), mono(ethenylacetonate) bis(ethylacetamidine acetate) aluminum (III), diisopropoxy mono(ethylacetamidine acetate) aluminum (III) or Plenact ( Registered trademark) Al-M (Kawasaki Precision Chemical Co., Ltd.) and other aluminum chelate compounds or bis(ethenylacetonate) magnesium (II), double (B) Magnesium sulphate acetate magnesium (II), isopropoxy mono(ethyl sulfonium acetonide) magnesium (II) or isopropoxy mono(ethyl acetamidine acetate) magnesium (II) Compound.

In the photosensitive resin composition of the present invention, the content of the (D) metal chelate compound is preferably 0.1 to 0.1 by weight based on 100 parts by weight of the total of the (A) acrylic resin and the (B) radical polymerizable compound. 10 parts by weight, more preferably 0.5 to 5 parts by weight. When the content of the (D) metal chelate compound is less than 0.1 part by weight, the effect of improving chemical resistance, vacuum resistance, moist heat resistance, or artificial sweat resistance may be insufficient. On the other hand, when it exceeds 10 parts by weight, there is a case where the transparency is lowered or the residue after development is caused, and the storage stability of the coating liquid is lowered.

The photosensitive resin composition of the present invention contains (E) a solvent. Further, as the solvent (E), a compound having an alcoholic hydroxyl group, a compound having a carbonyl group, or having three or more ethers is preferable in that the components can be uniformly dissolved and the transparency of the obtained cured film is improved. The compound of the bond or the like is more preferably a compound having a boiling point of 110 to 250 ° C at atmospheric pressure. When the boiling point is 110 ° C or more, the solvent is appropriately volatilized at the time of coating, and the coating film is dried to obtain a good coating film having no coating unevenness. On the other hand, when the boiling point is 250 ° C or lower, the amount of residual solvent in the coating film can be lowered, and the amount of film shrinkage during thermal curing can be reduced, whereby more excellent flatness can be obtained.

Examples of the compound having an alcoholic hydroxyl group and having a boiling point of 110 to 250 ° C at atmospheric pressure include, for example, hydroxyacetone, 4-hydroxy-2-butanone, 3-hydroxy-3-methyl-2-butanone, and 4 -hydroxy-3-methyl-2-butanone, 5-hydroxy-2-pentanone, 4-hydroxy-2-pentanone, 4-hydroxy-4-methyl-2-pentanone (diacetone Alcohol), methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol single n-Butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, propylene glycol mono-telebutyl ether, diethylene glycol monomethyl ether, diethyl Glycol monoethyl ether, diethylene glycol mono-n-propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methyl-1-butanol, tetrahydrofurfuryl alcohol, n-butanol or n-pentanol, but from the viewpoint of coatability, diacetone alcohol, ethyl lactate, and ethylene are preferred. Alcohol monomethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methyl- 1-butanol or tetrahydrofurfuryl alcohol.

Examples of the compound having a carbonyl group and having a boiling point of 110 to 250 ° C at atmospheric pressure include n-butyl acetate, isobutyl acetate, 3-methoxy-n-butyl acetate, and 3-methyl-3. -Methoxy-n-butyl acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, methyl n-butyl ketone, methyl isobutyl ketone, diisobutyl Ketone, 2-heptanone, acetoacetone, cyclopentanone, cyclohexanone, cycloheptanone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, propyl carbonate, N-methyl Pyrrolidone, N,N'-dimethylformamide, N,N'-dimethylacetamide or 1,3-dimethyl-2-imidazolidinone, but from the viewpoint of coating properties From the viewpoint of, it is preferably 3-methoxy-n-butyl acetate, propylene glycol monomethyl ether acetate or γ-butyrolactone.

Examples of the compound having three or more ether bonds and having a boiling point of 110 to 250 ° C at atmospheric pressure include diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol ethyl. Methyl ether, diethylene glycol Di-n-propyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol ethyl methyl ether or dipropylene glycol di-n-propyl ether, but from the viewpoint of coatability, it is preferably two Glycol dimethyl ether, diethylene glycol ethyl methyl ether or dipropylene glycol dimethyl ether.

The content of the solvent (E) in the photosensitive resin composition of the present invention can be appropriately adjusted according to the coating method, etc., but when the film is formed by, for example, spin coating, it is generally used as a photosensitive resin composition. 50 to 95% by weight of the whole.

The photosensitive resin composition of the present invention preferably further comprises (F) having a ring skeleton selected from the group consisting of an amine group, a mercaptoamine group, a urea group, a ketimine group, an isocyanate group, a mercapto group, and an iso-cyanuric acid ring. a decane compound of a substituent in the group of an acrylic group and a styryl group (hereinafter, "(F) decane compound"). The (F) decane compound preferably has an alkoxy group from the viewpoint of adhesion of the cured film. Since the photosensitive resin composition contains (F) a decane compound, the adhesion and chemical resistance of the obtained cured film can be improved. (F) a functional group of an amine group, a mercapto group, a ureido group, a ketimine group, an isocyanate group, a fluorenyl group, an iso-cyanuric acid ring skeleton, a (meth)acrylic group or a styryl group which the decane compound has. It is a site capable of reacting with a resin or the like, and functions as a site capable of coordinating on the surface of the substrate of the substrate in accordance with the functional group. Further, the (A) alkoxyalkyl group of the decane compound is converted into a stanol group by hydrolysis, and the stanol group can form a covalent bond with a hydroxyl group on the surface of the substrate of the substrate. It is presumed that the interaction between the cured film and the substrate of the substrate is increased by the action of the above, and the adhesion and chemical resistance of the obtained cured film are improved.

The (F) decane compound may, for example, be 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane or N-(2-aminoethyl)-3-aminopropyl Trimethoxy decane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyltriethyl Oxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxydecane hydrochloride, 3-(4-Aminophenyl)propyltrimethoxydecane, 1-[4-(3-trimethoxydecylpropyl)phenyl]urea, 1-(3-trimethoxydecylpropyl) Urea, 1-(3-triethoxydecylpropyl)urea, 3-trimethoxydecyl-N-(1,3-dimethylbutylidene)propylamine, 3-triethoxydecylalkyl -N-(1,3-dimethylbutylidene)propylamine, 3-isocyanatepropyltrimethoxydecane, 3-isocyanatepropyltriethoxydecane, 3-isocyanatepropylmethyldiethoxylate Base decane, 1,3,5-gin(3-trimethoxydecylpropyl)isocyano cyanide, 1,3,5-gin(3-triethoxydecylpropyl)isocyanide Acid, 3-mercaptopropyltrimethoxydecane, 3-mercaptopropyltri Oxydecane, 3-mercaptopropylmethyldimethoxydecane, 3-(methyl)propenyloxypropyltrimethoxydecane, 3-(methyl)propenyloxypropyltriethoxy Decane, 3-(meth)acryloxypropylmethyldimethoxydecane, 3-(methyl)propenyloxypropylmethyldiethoxydecane, 4-styryltrimethoxy Decane or 4-styryltriethoxydecane.

In the photosensitive resin composition of the present invention, the content of the (F) decane compound is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the total of the (A) acrylic resin and the (B) radical polymerizable compound. More preferably, it is 0.5 to 7 parts by weight. If the content of the (F) decane compound is less than 0.1 parts by weight, the effect of improving adhesion or chemical resistance may be insufficient. Happening. On the other hand, when it exceeds 10 parts by weight, the residue after development may be caused, and the storage stability of the coating liquid may be lowered.

The photosensitive resin composition of the present invention preferably further contains (G) a maleimide compound. As the (G) maleimide compound, a general maleimide or maleimide derivative can be used. Since the photosensitive resin composition contains the (G) maleimide compound, the storage stability of the coating liquid can be improved, and the chemical resistance, vacuum resistance, moist heat resistance, and artificial sweat resistance of the obtained cured film can be improved. It is estimated that the structure derived from maleimide in the (G) maleimide compound contributes to the stabilization of the photosensitive resin composition, and suppresses the progress of the reaction in the storage of the coating liquid, thereby suppressing the resistance. Reduction in drug properties, adhesion, etc. It is presumed that the (G) maleimide compound is incorporated as a part of the three-dimensional network structure by heat reaction with a resin or the like, and the crosslinking density is increased. Further, it is considered that the structure derived from maleimide of the (G) maleimide compound acts as a site capable of coordinating on the surface of the substrate of the substrate, and the cured film obtained has improved chemical resistance. Further, it is considered that the vacuum resistance, the moist heat resistance and the artificial sweat resistance of the obtained cured film are improved by the improvement of the crosslinking density. The (G) maleimide compound preferably has an aromatic cyclic skeleton or an aliphatic cyclic skeleton. It is considered that the cured film has chemical resistance, vacuum resistance, moist heat resistance, artificial sweat resistance and heat resistance by the hydrophobicity or chemical stability of the aromatic cyclic skeleton or the aliphatic cyclic skeleton. Upgrade.

Examples of the (G) maleimide compound include maleic imine, N-methyl maleimide, N-ethyl maleimide, and N-n-propyl malayan. Amine, N-isopropylmaleimide, N-n-butylmalay Yttrium, N-tert-butylmaleimide, N-n-hexylmaleimide, N-dido-maleimide, N-cyclopentylmaleimide, N- Cyclohexylmaleimide, N-(2,4-dimethylcyclohexyl)maleimide, N-vinylmaleimide, N-(meth)acrylic acid maleimide , N-methoxymethyl maleimide, N-(2-ethoxyethyl)maleimide, N-(4-butoxyethyl)maleimide, N- [(Meth) propylene methoxymethyl] maleimine, N-[2-(methyl) propylene methoxyethyl] maleimine, N-[3-(methyl) propylene醯oxypropyl]maleimide, N-methoxycarbonylmaleimide, N-(3-methoxycarbonylpropyl)maleimide, N-(2-hydroxyethyl ) maleimide, N-(4-hydroxy-n-butyl)maleimide, N-(2-carboxyethyl)maleimide, N-(3-carboxypropyl)male Yttrium, N-(5-carboxypentyl)maleimide, N-phenylmaleimide, N-(4-methylphenyl)maleimide, N-(3- Methylphenyl)maleimide, N-(2-methylphenyl)maleimide, N-(2,6-dimethylphenyl)maleimide, N-(2 ,6-diethyl Methyl quinone imine, N-(4-styryl) maleimide, N-(4-methoxyphenyl) maleimide, N-(3-methoxyphenyl ) maleimide, N-(2-methoxyphenyl)maleimide, N-(4-methoxycarbonylphenyl)maleimide, N-(4-hydroxyphenyl) ) maleimide, N-(3-hydroxyphenyl)maleimide, N-(2-hydroxyphenyl)maleimide, N-(4-carboxyphenyl)malaya Amine, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-(1-naphthyl)maleimide, N- Benzyl maleimide, N-(2-phenylethyl)maleimide, N-(9-acridinyl)maleimide, N-[4-(2-benzimidazole Phenyl]maleimide, 3-maleimide propionic acid N-succinimide, 4-maleimine butyric acid N-succinimide, 11-male Asian Amine lauric acid N-succinimide, 6-maleimide caproic acid N-succinimide, 4-(N-maleimidomethyl)cyclohexanecarboxylic acid N-amber N-amino, 4-(4-maleimidophenyl)butyric acid N-succinimide or 3-maleimide benzoic acid N-succinimide, but resistant to hardened film From the viewpoints of improvement in drug properties, vacuum resistance, moist heat resistance, artificial sweat resistance and heat resistance, N-cyclopentylmaleimide, N-cyclohexylmaleimide, N-(2) are preferred. ,4-dimethylcyclohexyl)maleimide, N-phenylmaleimide, N-(4-methylphenyl)maleimide, N-(3-methylphenyl ) maleimide, N-(2-methylphenyl)maleimide, N-(2,6-dimethylphenyl)maleimide, N-(2,6-di Ethylphenyl)maleimide, N-(4-styryl)maleimide, N-(4-methoxyphenyl)maleimide, N-(3-methoxy Phenyl) maleimide, N-(2-methoxyphenyl)maleimide, N-(4-methoxycarbonylphenyl)maleimide, N-(4- Hydroxyphenyl)maleimide, N-(3-hydroxyphenyl)maleimide, N-(2-hydroxyphenyl)maleimide, N- (4-carboxyphenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-(1- Naphthyl)maleimide, N-benzylmaleimide or N-(2-phenylethyl)maleimide.

Further, the maleic imine compound is more preferably a bismaleimine compound represented by any one of the formulas (3) to (5). The bismaleimide compound has two structures derived from maleimine, each having two sites incorporated as part of a ternary mesh structure, and capable of coordinating on the substrate surface of the substrate. The part. Therefore, it is considered that the crosslinking density or the adhesion to the substrate surface of the substrate is further improved, and the chemical resistance, vacuum resistance, and moist heat resistance of the obtained cured film can be further improved. Sexual and artificial sweat resistance. The bismaleimine compound preferably has an aromatic cyclic skeleton or an aliphatic cyclic skeleton. It is considered that the chemical resistance, vacuum resistance, moist heat resistance, artificial sweat resistance and heat resistance of the obtained cured film are further improved by the hydrophobicity or chemical stability of the aromatic cyclic skeleton or the aliphatic cyclic skeleton. Upgrade.

(X represents an alkylene chain having 1 to 10 carbon atoms or an extended aryl chain having 6 to 15 carbon atoms. R ⁵ to R ¹⁰ each independently represent hydrogen, an alkyl group having 1 to 10 carbon atoms, and a carbon number of 1 to 6 The alkoxy group or the hydroxyl group, l, m, n and o each independently represent an integer of 1 to 4).

X is preferably an alkylene chain having 1 to 6 carbon atoms or an extended aryl chain having 6 to 10 carbon atoms, and R ⁵ to R ^{10 are} preferably independently hydrogen, alkyl having 1 to 6 carbon atoms, and carbon number. 1 to 4 alkoxy groups or hydroxyl groups. The alkylene chain, the extended aryl chain, the alkyl group and the alkoxy group described above may also be either an unsubstituted or substituted one.

Examples of the bismaleimide compound include 1,2-bis(maleimide)ethane, 1,3-bis(maleimide)propane, and 1,4-bis (Malay).醯imino)butane, 1,5-bis(maleimide)pentane, 1,6-bis(maleimide)hexane, 2,2,4-trimethyl-1,6 - bis (maleimide) hexane, N,N'-1,3-phenylene bis(maleimide), 4-methyl-N,N'-1,3-phenylene Bis(maleimide), N,N'-1,4-phenylene bis(maleimide), 3-methyl-N,N'-1,4-phenylene double (horse醯iimine), 4,4'-bis (maleimide) diphenylmethane, 3,3'-diethyl-5,5'-dimethyl-4,4'-double (horse Diphenylmethane or 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, which has chemical resistance, vacuum resistance, heat and humidity resistance from a cured film, From the viewpoint of improvement in artificial sweat resistance and heat resistance, 4,4'-bis(maleimide)diphenylmethane, 3,3'-diethyl-5,5'-dimethyl group is preferred. -4,4'-bis(maleimide)diphenylmethane or 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane.

In the photosensitive resin composition of the present invention, the content of the (G) maleimide compound is preferably 100 parts by weight based on the total of the (A) acrylic resin and the (B) radical polymerizable compound. 0.1 to 20 parts by weight, more preferably 1 to 15 parts by weight. When the (G) maleic imine compound is less than 0.1 part by weight, the effect of improving chemical resistance, vacuum resistance, moist heat resistance, artificial sweat resistance or heat resistance may be insufficient. On the other hand, if it is more than 20 parts by weight, there may be a cause of residue after development.

The photosensitive resin composition of the present invention preferably further contains (B2) a radically polymerizable compound having an anthracene skeleton. And (B2) has a tibia The radically polymerizable compound of the shelf refers to a compound having an anthracene skeleton and a plurality of ethylenically unsaturated double bond groups in the molecule. The (B2) radically polymerizable compound having an anthracene skeleton may, for example, be a compound represented by the formula (6), but is preferably a radical polymerization of a (meth)acryl group which is easily subjected to radical polymerization. Sex compounds. By the irradiation of light, the radical generated by the (C) photopolymerization initiator and (B2) the polymerization of the radically polymerizable compound having an anthracene skeleton, the exposed portion of the photosensitive resin composition is insolubilized in the alkaline aqueous solution. And can form a pattern. Moreover, since the (B2) radically polymerizable compound having an anthracene skeleton is contained, the obtained cured film can be improved in chemical resistance, vacuum resistance, moist heat resistance, artificial sweat resistance, and heat resistance. It is presumed that the chemical resistance, vacuum resistance, moist heat resistance, artificial sweat resistance, and heat resistance of the obtained cured film are improved by the hydrophobicity or chemical stability of the (B2) radical polymerizable compound having an anthracene skeleton. . The double bond equivalent of the (B2) radically polymerizable compound having an anthracene skeleton is preferably from 200 to 500 g/mol from the viewpoint of the sensitivity at the time of exposure and the hardness of the cured film.

(X represents direct bonding or oxygen. When X represents direct bonding, Y also represents direct bonding. When X is oxygen, Y represents an alkyl chain having a carbon number of 1 to 10. R ¹¹ and R ¹² are independent The ground represents an alkenyl group having 2 to 7 carbon atoms or an alkenyloxy group having 2 to 7 carbon atoms. R ¹³ to R ¹⁶ each independently represent hydrogen, an alkyl group having 1 to 10 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. Or hydroxy).

When X is oxygen, Y is preferably an alkylene chain having 1 to 6 carbon atoms. R ¹¹ and R ¹² are each independently independently an alkenyl group having 2 to 5 carbon atoms or an alkenyloxy group having 2 to 5 carbon atoms. R ¹³ to R ^{16 are} preferably an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a hydroxyl group. The above alkyl chain, alkenyl group, alkenyloxy group, alkyl group and alkoxy group may also be either unsubstituted or substituted.

Examples of the (B2) radical polymerizable compound containing an anthracene skeleton include Ogsol (registered trademark) EA-50P, EA-0200, EA-0250P, EA-500, EA-1000, and EA-. F5003, with EA-F5503 or with EA-F5510 (all of which are manufactured by Osaka Gas Chemical Co., Ltd.), 9,9-bis[4-(2-(methyl)acryloxyethoxyethoxy)phenyl] Ruthenium, 9,9-bis[4-(3-(methyl)propenyloxypropoxy)phenyl]anthracene, 9,9-bis[4-(2-(methyl)propenyloxy) Oxy)-3-methylphenyl]anthracene, 9,9-bis[4-(2-(methyl)acryloxyethoxyethoxy)-3,5-dimethylphenyl]anthracene or 9 , 9-bis(4-(methyl)acryloxyphenyl) hydrazine.

In the photosensitive resin composition of the present invention, the content of the (B2) radical polymerizable compound having an anthracene skeleton is 100 parts by weight based on the total of the (A) acrylic resin and the (B) radical polymerizable compound. It is preferably 0.1 to 20 parts by weight, more preferably 1 to 10 parts by weight. When the (B2) radical polymerizable compound having an anthracene skeleton is less than 0.1 part by weight, the effect of improving chemical resistance, vacuum resistance, moist heat resistance, artificial sweat resistance or heat resistance may be insufficient. On the other hand, when it is more than 20 parts by weight, the hardness of the residue after curing or the cured film may be lowered.

The photosensitive resin composition of the present invention preferably further contains (B3) a radically polymerizable compound having a carboxyl group. Further, (B3) a radically polymerizable compound having a carboxyl group means a compound having a carboxyl group in a molecule and a plurality of ethylenically unsaturated double bond groups. The (B3) radical-polymerizable compound having a carboxyl group may, for example, be a compound represented by the formula (7) or (8), but is preferably a (meth)acryl-based group which is easily subjected to radical polymerization. A radical polymerizable compound. By the irradiation of light, the radical generated by the (C) photopolymerization initiator and (B3) the polymerization of the radical polymerizable compound having a carboxyl group are carried out, and the exposed portion of the photosensitive resin composition is insolubilized in the alkaline aqueous solution. And can form a pattern. In addition, since (B3) a radically polymerizable compound having a carboxyl group is contained, generation of residue after development can be suppressed, and high resolution can be ensured. It is estimated that the solubility of the alkaline developing solution is improved by the carboxyl group of the (B3) radical polymerizable compound having a carboxyl group, and the residue after development is suppressed. The double bond equivalent of the radically polymerizable compound is preferably from 80 to 400 g/mol from the viewpoint of the sensitivity at the time of exposure and the hardness of the cured film.

(X represents an alkylene chain having 1 to 10 carbon atoms, an alkylene chain having 2 to 12 carbon atoms having one ethylenically unsaturated double bond, a cycloalkyl chain having a carbon number of 4 to 10 or a carbon number of 6 An extended aryl group of ~15. R ¹⁷ to R ²⁴ each independently represent an alkenyl group having 2 to 7 carbon atoms or an alkenyloxy group having 2 to 7 carbon atoms.

X is preferably an alkylene chain having 1 to 6 carbon atoms, an alkylene chain having 2 to 8 carbon atoms having one ethylenically unsaturated double bond, a cyclic alkyl chain having 4 to 7 carbon atoms or a carbon number. 6~10 aryl chain. R ¹⁷ to R ²⁴ are each independently independently an alkenyl group having 2 to 5 carbon atoms or an alkenyloxy group having 2 to 5 carbon atoms. The alkylene chain, the extended alkyl chain, the extended aryl chain, the alkenyl group and the alkenyloxy group may be either an unsubstituted or substituted one.

(B3) a carboxyl group-containing radical polymerizable compound by reacting a hydroxyl group-containing unsaturated compound having a hydroxyl group and a plurality of ethylenically unsaturated double bond groups in a molecule with a compound having an acid anhydride group in a molecule Got it.

The hydroxyl group-containing unsaturated compound having one or more hydroxyl groups and a plurality of ethylenically unsaturated double bond groups in the molecule may, for example, be trimethylolpropane di(meth)acrylate or decyltrimethylol. Propane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol di(meth)acrylate Dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate or dipentaerythritol penta(meth)acrylate.

The compound having an acid anhydride group in the molecule may, for example, be succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride or tetrahydrophthalic anhydride, but is preferably succinic anhydride.

Examples of the (B3) radical polymerizable compound having a carboxyl group include, for example, Aronix (registered trademark) M-510 or the same M-520 (all of which are manufactured by East Asia Synthetic Co., Ltd.), and succinic acid mono [2, 2, 2-paran ((meth)propenyloxymethyl)ethyl]ester or succinic acid mono[2,2-bis((methyl)acryloxymethyl)-3-[2,2,2 - cis ((meth) propylene methoxymethyl) ethoxy] propyl] ester.

In the photosensitive resin composition of the present invention, the content of the radically polymerizable compound having a carboxyl group in (B3) is 100 parts by weight based on the total of the (A) acrylic resin and the (B) radical polymerizable compound. Preferably, it is 1 to 40 parts by weight, more preferably 5 to 30 parts by weight. When the (B3) radical polymerizable compound having a carboxyl group is less than 1 part by weight, the effect of suppressing the residue after development may be insufficient. On the other hand, when it is more than 40 parts by weight, the hardness of the cured film may be lowered or the chemical resistance may be lowered.

The photosensitive resin composition of the present invention preferably further contains a (H) ruthenium compound. The (H) hydrazine compound may, for example, be a compound represented by any one of the formulae (9) to (12). By containing the (H) antimony compound, the obtained cured film can be improved in chemical resistance, vacuum resistance, moist heat resistance, artificial sweat resistance, and heat resistance. It is presumed that the (H) ruthenium compound is incorporated as part of the ternary mesh structure by the reaction of heat with a resin or the like. Further, it is presumed that the chemical resistance, vacuum resistance, moist heat resistance, artificial sweat resistance, and heat resistance of the obtained cured film are improved by the hydrophobicity or chemical stability of the ruthenium skeleton of the (H) ruthenium compound.

(X represents direct bonding or oxygen. When X represents direct bonding, Y also represents direct bonding. When X is oxygen, Y represents an alkyl chain having a carbon number of 1 to 10. R ²⁵ and R ²⁶ are independent. The ground represents a glycidoxy group, a hydroxyl group or an amine group. R ²⁷ to R ³⁰ each independently represent hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or a hydroxyl group).

When X is oxygen, Y is preferably an alkylene chain having 1 to 6 carbon atoms. R ²⁵ to R ³⁰ are each independently an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a hydroxyl group. The above alkyl chain, alkyl group and alkoxy group may also be either unsubstituted or substituted.

Examples of the (H) hydrazine compound include Ogsol (registered trademark) PG, the same PG-100, the same EG, the same EG-200, the same EG-210 (all of which are manufactured by Osaka Gas Chemical Co., Ltd.), and Oncoat (registered). Trademark) EX-1010, same as EX-1011, with EX-1012, with EX-1020, with EX-1030, with EX-1040, with EX-1050, with EX-1051, with EX-1020M80 or with EX- 1020M70 (all of which are manufactured by Nagase Chemtex), 9,9-bis[4-(2-epoxypropoxyethoxy)phenyl]anthracene, 9,9-bis[4-(3-epoxy) Propoxy Propyloxy)phenyl]anthracene, 9,9-bis[4-(2-epoxypropoxyethoxy)-3-methylphenyl]anthracene, 9,9-bis[4-(2 -glycidoxyethoxy)-3,5-dimethylphenyl]anthracene, 9,9-bis(4-glycidoxyphenyl)anthracene, 9,9-bis(4-ring Oxypropoxy-3-methylphenyl)indole, 9,9-bis(4-epoxypropoxy-3,5-dimethylphenyl)anthracene, 9,9-bis[4-(2 -hydroxyethoxy)phenyl]anthracene, 9,9-bis[4-(3-hydroxypropoxy)phenyl]anthracene, 9,9-bis[4-(2-hydroxyethoxy)-3 -Methylphenyl]anthracene, 9,9-bis[4-(2-hydroxyethoxy)-3,5-dimethylphenyl]anthracene, 9,9-bis(4-hydroxyphenyl)anthracene 9,9-bis(4-hydroxy-3-methylphenyl)anthracene, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)anthracene, 9,9-bis (4- Aminophenyl)anthracene, 9,9-bis(4-amino-3-methylphenyl)anthracene, 9,9-bis(4-amino-3,5-dimethylphenyl)anthracene, 9,9-bis(4-epoxypropoxy-1-naphthyl)anthracene, 9,9-bis(5-epoxypropoxy-1-naphthyl)anthracene, 9,9-bis (6- Epoxypropoxy-2-naphthyl)anthracene, 9,9-bis[2-epoxypropoxy-(1,1'-biphenyl)-5-yl]anthracene, 9,9-double [ 3-glycidoxy-(1,1'-biphenyl)-5-yl]indole or 9,9-bis[4'-glycidoxy-(1,1'-biphenyl) -4-base]茀, etc. From the viewpoint of improvement in chemical resistance, vacuum resistance, moist heat resistance and artificial sweat resistance of the cured film, Ogsol (registered trademark) PG, same PG-100, same EG, same EG-200, and EG- are preferable. 210 or the same EG-250" (all above Osaka Gas Chemical Co., Ltd.), Oncoat (registered trademark) EX-1010, with EX-1011, with EX-1012, with EX-1020, with EX-1030, the same EX-1040, same as EX-1050, with EX-1051, with EX-1020M80 or with EX-1020M70 (all of which are manufactured by Nagase Chemtex), 9,9-bis[4-(2-epoxypropoxygen) Ethyl ethoxy)phenyl]anthracene, 9,9-bis[4-(3-epoxypropoxypropoxy)phenyl]anthracene, 9,9-bis[4-(2-epoxypropoxygen) Ethyl ethoxy)-3-methylphenyl]anthracene, 9,9-bis[4-(2-epoxypropoxyethoxy)-3,5-dimethylphenyl]anthracene, 9, 9-double (4- Glycidoxyphenyl)anthracene, 9,9-bis[4-(2-hydroxyethoxy)phenyl]anthracene, 9,9-bis[4-(3-hydroxypropoxy)phenyl] Ruthenium, 9,9-bis(4-epoxypropoxy-1-naphthyl)anthracene, 9,9-bis(5-epoxypropoxy-1-naphthyl)anthracene, 9,9-bis ( 6-glycidoxy-2-naphthyl)anthracene, 9,9-bis[2-epoxypropoxy-(1,1'-biphenyl)-5-yl]anthracene, 9,9- Bis[3-epoxypropoxy-(1,1'-biphenyl)-5-yl]anthracene or 9,9-bis[4'-glycidoxy-(1,1'-biphenyl) Base)-4-yl]茀.

In the photosensitive resin composition of the present invention, the content of the (H) ruthenium compound is preferably from 1 to 30 by weight based on 100 parts by weight of the total of the (A) acrylic resin and the (B) radical polymerizable compound. More preferably, it is 5 to 25 parts by weight. When the (H) bismuth compound is less than 1 part by weight, the effect of improving chemical resistance, vacuum resistance, moist heat resistance, artificial sweat resistance or heat resistance may be insufficient. On the other hand, when it is more than 30 parts by weight, the residue after development may be caused, and the storage stability of the coating liquid may be lowered.

The photosensitive resin composition of the present invention preferably further contains (I) a polyfunctional epoxy compound. The (I) polyfunctional epoxy compound may, for example, be a compound represented by any one of the formulae (13) to (18). By containing the (I) polyfunctional epoxy compound, the obtained cured film can be improved in chemical resistance, vacuum resistance, moist heat resistance, artificial sweat resistance, and heat resistance. It is presumed that the epoxy group of the (I) polyfunctional epoxy compound is incorporated as part of the three-dimensional network structure by heat reaction with a resin or the like. Further, it is presumed that the chemical resistance, vacuum resistance, moist heat resistance, and artificial sweat resistance of the obtained cured film are obtained by the hydrophobicity or chemical stability of the aromatic cyclic skeleton of the (I) polyfunctional epoxy compound. Increased heat resistance.

(R ³¹ to R ⁴⁰ and R ⁴³ to R ⁴⁸ each independently represent hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or a hydroxyl group. R ⁴¹ , R ⁴² and R ⁴⁹ are each independently It represents hydrogen, an alkyl group having 1 to 10 carbon atoms or a carbon number of 6 to 15 aryl groups.

R ³¹ to R ⁴⁰ and R ⁴³ to R ⁴⁸ are each independently hydrogen, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a hydroxyl group. R ⁴¹ , R ⁴² and R ⁴⁹ are each independently independently hydrogen, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms. The above alkyl group, alkoxy group and aryl group may also be either an unsubstituted or substituted one.

As the (I) polyfunctional epoxy compound, for example, 1,1- Bis(4-glycidoxyphenyl)-1-[4-[1-(4-epoxypropoxyphenyl)-1-methylethyl]phenyl]ethane, 2,2- Bis(4-glycidoxyphenyl)propane, 1,1-bis(4-glycidoxyphenyl)-1-phenylethane, 1,1,1-parade (4-epoxy Propoxyphenyl)methane, 1,1,1-gin(4-glycidoxyphenyl)ethane, 1,1-bis(4-epoxypropoxyphenyl)-1-(1) -naphthyl)ethane, 1,1-bis(4-epoxypropoxyphenyl)-1-(2-naphthyl)ethane, 1,1-bis(4-epoxypropoxy-1 -naphthyl)-1-(4-epoxypropoxyphenyl)ethane, 1,1-bis(5-epoxypropoxy-1-naphthalenyl)-1-(4-epoxypropoxylate Ethylphenyl)ethane, 1,1-bis(6-epoxypropoxy-2-naphthalenyl)-1-(4-epoxypropoxyphenyl)ethane, 1,1-double [2 -glycidoxy-(1,1'-biphenyl)-5-yl]-1-(4-epoxypropoxyphenyl)ethane, 1,1-bis[3-epoxypropane Oxy-(1,1'-biphenyl)-5-yl]-1-(4-epoxypropoxyphenyl)ethane or 1,1-bis[4'-glycidoxy- (1,1'-Biphenyl)-4-yl]-1-(4-epoxypropoxyphenyl)ethane.

In the photosensitive resin composition of the present invention, the content of the (I) polyfunctional epoxy compound is preferably 1 when the total of the (A) acrylic resin and the (B) radical polymerizable compound is 100 parts by weight. ~30 parts by weight, more preferably 5 to 25 parts by weight. When the (I) polyfunctional epoxy compound is less than 1 part by weight, the effects of improving chemical resistance, vacuum resistance, moist heat resistance, artificial sweat resistance, or heat resistance may be insufficient. On the other hand, when it is more than 30 parts by weight, the residue after development may be caused, and the storage stability of the coating liquid may be lowered.

The photosensitive resin composition of the present invention may further contain an isocyanate compound. In the isocyanate compound referred to herein, a blocked isocyanate compound in which an isocyanate group is blocked is contained. Since the photosensitive resin composition contains an isocyanate compound, the resulting hard can be obtained The chemical resistance, vacuum resistance, moist heat resistance and artificial sweat resistance of the film are improved. It is presumed that the isocyanate group is capable of reacting with a carboxyl group or the like in the resin by heat, and the isocyanate compound has a function as a crosslinking agent. Further, it is presumed that the isocyanate compound has a function as a crosslinking agent, and the film density of the cured film increases, and the obtained cured film is improved in chemical resistance, vacuum resistance, moist heat resistance, and artificial sweat resistance.

The isocyanate compound may, for example, be hexamethylene diisocyanate, isophorone diisocyanate, toluene-2,6-diisocyanate, methylene diphenyl-4,4'-diisocyanate or dicyclohexylmethane- 4,4'-diisocyanate, 1,3-bis(isocyanatemethyl)benzene, 1,3-bis(isocyanatemethyl)cyclohexane, norbornane diisocyanate, naphthalene-1,5-diisocyanate , polymethylene polyphenyl polyisocyanate, 2-isocyanate ethyl (meth) acrylate, 2-[[[[(1-methylpropylidene))] oxy]carbonyl]amino] Ethyl (meth) acrylate, 2-[[(3,5-dimethylpyrazolyl)carbonyl]amino]ethyl (meth) acrylate, 1,1-(bis(meth) propylene醯oxymethyl)ethyl isocyanate, hexamethylene (6-isocyanate hexyl)isocyano cyanide, ginseng (3-isocyanate methyl-3,5,5-trimethylcyclohexyl)isocyanuric acid 1,3,5-gin (6-isocyanate hexyl) biuret, Duranate (registered trademark) MF-K60B, same SBN-70D, same MF-B60B, same 17B-60P, same 17B-60PX, same TPA -B80E, same as TPA-B80X, same as E402-B80B or the same E402-B80T (all of which are manufactured by Asahi Kasei Chemicals Co., Ltd.) or Aqua BI 200, Aqua BI220, BI7950, BI7951, BI7960, BI7961, BI7962, BI7990, BI7991 or BI7992 (all manufactured by Baxenden), preferably 2-isocyanate ethyl (A) from the viewpoint of hardness improvement of the cured film Acrylate, 2-[[[[(1-methyl)propyl)amino]oxy Alkyl]carbonyl]amino]ethyl(meth)acrylate, 2-[[(3,5-dimethylpyrazolyl)carbonyl]amino]ethyl(meth)acrylate or 1,1- (bis(methyl)acryloxymethyl)ethyl isocyanate. Further, from the viewpoint of improving the moist heat resistance and the artificial sweat resistance of the cured film, ginseng (6-isocyanate hexyl) isocyanuric acid, ginseng (3-isocyanate methyl-3, 5, 5 is preferred). - Trimethylcyclohexyl)isocyano cyanide or 1,3,5-gin (6-isocyanate hexyl) biuret.

When the content of the isocyanate compound in the photosensitive resin composition of the present invention is 100 parts by weight based on the total of the (A) acrylic resin and the (B) radical polymerizable compound, it is preferably 0.1 to 10 parts by weight. It is preferably 0.5 to 7 parts by weight. When the amount of the isocyanate compound is less than 0.1 part by weight, the effect of improving chemical resistance, vacuum resistance, moist heat resistance, or artificial sweat resistance may be insufficient. On the other hand, when it is more than 10 parts by weight, the residue after development may be caused, and the storage stability of the coating liquid may be lowered.

The photosensitive resin composition of the present invention may further contain a urea compound having an ethylenically unsaturated double bond group. Since the urea compound having an ethylenically unsaturated double bond group is contained, the obtained cured film can be improved in chemical resistance, vacuum resistance, moist heat resistance, and artificial sweat resistance. It is presumed that the urea site is capable of reacting with a resin or the like by heat, and has a function as a site capable of coordinating on the surface of the substrate. In addition, it is presumed that the ethylenically unsaturated double bond group is bonded to the ethylenically unsaturated double bond group which is bonded to a resin or the like and is polymerized by radical polymerization to form a crosslinked structure. Further, it is presumed that since the urea compound having an ethylenically unsaturated double bond group functions as a crosslinking agent, the film density of the cured film increases, and the obtained cured film is resistant to chemicals, vacuum resistance, moist heat resistance, and artificial sweat. Increased patience.

Examples of the urea compound having an ethylenically unsaturated double bond group include 1-allyl urea, 1-vinyl urea, 1-allyl-2-thiourea, and 1-vinyl-2-thiourea. , 1-allyl-3-methyl-2-thiourea, 1-allyl-3-(2-hydroxyethyl)-2-thiourea or 1-methyl-3-(4-vinyl Phenyl)-2-thiourea.

When the content of the urea compound having an ethylenically unsaturated double bond group in the photosensitive resin composition of the present invention is 100 parts by weight based on the total of the (A) acrylic resin and the (B) radical polymerizable compound, It is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 7 parts by weight. When the amount of the urea compound having an ethylenically unsaturated double bond group is less than 0.1 part by weight, the effect of improving chemical resistance, vacuum resistance, moist heat resistance, or artificial sweat resistance may be insufficient. On the other hand, when it is more than 10 parts by weight, the residue after development may be caused, and the storage stability of the coating liquid may be lowered.

The photosensitive resin composition of the present invention may further contain a polymerization inhibitor. Since an appropriate amount of a polymerization inhibitor is contained, generation of residue after development can be suppressed, and high resolution can be ensured. It is presumed that the polymerization inhibitor suppresses excessive radicals generated from the (C) photopolymerization initiator by irradiation with light during exposure, and it is possible to suppress the progress of excessive radical polymerization.

The polymerization inhibitor may, for example, be di-tert-butylhydroxytoluene, butylhydroxyanisole, hydroquinone, 4-methoxyphenol, 1,4-benzoquinone or t-butylcatechol. Moreover, as a commercially available polymerization inhibitor, for example, IRGANOX (registered trademark) 1010, same as 1035, the same 1076, the same 1098, the same 1135, the same 1330, the same 1726, the same 1425, the same 1520 245, 259, 3114, 565 or 295 (all above BASF).

The photosensitive resin composition of the present invention may further contain an ultraviolet absorber. Since an appropriate amount of the ultraviolet absorber is contained, the occurrence of residue after development can be suppressed, and the high resolution can be ensured, and the light resistance of the obtained cured film can be improved. It is presumed that the ultraviolet absorber can suppress the progress of excessive radical polymerization because the scattered light or the reflected light which is generated when the light is irradiated during exposure is captured. Further, it is presumed that in the obtained cured film, the ultraviolet ray absorbing agent also captures the irradiated light, and the light resistance is improved.

As the ultraviolet absorber, a benzotriazole compound, a diphenyl ketone compound or a trisole is preferred from the viewpoint of transparency and non-coloring property. Compounds, etc.

The benzotriazole compound may, for example, be 2-(2'-hydroxyphenyl)-2H-benzotriazole or 2-(2'-hydroxy-5'-methylphenyl)-2H-benzo. Triazole, 2-(2'-hydroxy-5'-tert-butylphenyl)-2H-benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methyl Phenyl)-2H-benzotriazole, 2-[2'-hydroxy-3',4'-bis(1-methyl-1-phenylethyl)phenyl]-2H-benzotriazole, 2-(2'-hydroxy-3',5'-di-third-pentylphenyl)-2H-benzotriazole, 2-(2'-hydroxy-5'-trioctylphenyl)-2H -benzotriazole, 2-(2'-hydroxy-3'-dodecy-5'-methylphenyl)-2H-benzotriazole, 2-[2'-hydroxy-5'-(1 ,1,3,3-tetramethylbutyl)phenyl]-2H-benzotriazole, 2-[2'-hydroxy-3'-(1-methyl-1-phenylethyl)-5 '-(1,1,3,3-Tetrabutylbutyl)phenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-(2-methylpropenyloxyethyl) Phenyl]-2H-benzotriazole or [3-(2H-benzotriazol-2-yl)-4-hydroxy-5- Octyl butyl phenyl] propionate.

The diphenylketone compound may, for example, be 2-hydroxy-4-methoxydiphenyl ketone or 2-hydroxy-4-octyloxydiphenyl ketone.

As three The compound may, for example, be 2-(2'-hydroxy-4'-hexyloxyphenyl)-4,6-diphenyl-1,3,5-tri ,2-[2'-hydroxy-4'-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-bis(2',4'-dimethylphenyl) -1,3,5-three ,2-[2'-hydroxy-4'-[2-hydroxy-3-(2-ethylhexyloxy)propoxy]phenyl]-4,6-bis(2',4'-dimethyl Phenyl)-1,3,5-three Or 2,4-bis(2'-hydroxy-4'-butoxyphenyl)-6-(2',4'-dibutoxy)-1,3,5-three .

The photosensitive resin composition of the present invention may further contain a surfactant. By containing an appropriate amount of the surfactant, the leveling property at the time of coating is improved, and uneven coating can be suppressed, and a uniform coating film can be obtained.

The surfactant may, for example, be a fluorine-based surfactant, a rhodium-based surfactant, a polyalkylene oxide-based surfactant, or a poly(meth)acrylate-based surfactant.

The fluorine-based surfactant may, for example, be 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl)ether or 1,1,2,2-tetrafluorooctane. Hexyl hexyl ether, octaethylene glycol bis(1,1,2,2-tetrafluorobutyl)ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl)ether, eight Propylene glycol bis(1,1,2,2-tetrafluorobutyl)ether, hexapropanediol bis(1,1,2,2,3,3-hexafluoropentyl)ether, sodium perfluorododecylsulfonate, 1,1,2,2,8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, N-[3-(all Fluoxetane sulfonamide) propyl]-N,N'-dimethyl-N-carboxymethylene ammonium betaine, perfluoroalkylsulfonamide propyltrimethylammonium salt , perfluoroalkyl-N-ethylsulfonyl glycinate or bis(N-perfluorooctylsulfonyl-N-ethylaminoethyl) phosphate. Further, a compound having a fluoroalkyl group or a fluorine-extended alkyl chain at the terminal of the monoperfluoroalkylethyl phosphate or the like, and at any of the main chain and the side chain may be mentioned. Examples of such a compound include Megafac (registered trademark) F-142D, the same F-172, the same F-173, the same F-183, the same F-444, the same F-445, the same F-470, and the same F. -475, with F-477, with F-555 or with F-559" (all of them are from Japan Ink Chemical Industry Co., Ltd.), Eftop (registered trademark) EF301, with 303 or 352 (all of them are Mitsubishi materials) Electronic (share) system, Fluorad (registered trademark) FC-430 or FC-431 (above Sumitomo 3M (share) system), Asahiguard (registered trademark) AG710 (Asahi Glass Co., Ltd.), Surflon ( Registered trademark) S-382, "with SC-101, with SC-102, with SC-103, with SC-104, with SC-105 or with SC-106 (all above AGC Seimchemical), BM -1000 or BM-1100 (all of which are based on Yushang) or NBX-15, FTX-218 or DFX-218 (all of which are NEOS).

Examples of the rhodium-based surfactant include SH28PA, SH7PA, SH21PA, SH30PA, or ST94PA (all of which are manufactured by Toray Dow Corning Co., Ltd.) or BYK-301, BYK-307, BYK-331, and BYK-333. It is BYK-345 (all of them are BYK Chemical Japan).

The content of the surfactant in the photosensitive resin composition of the present invention is generally preferably 0.0001 to 1% by weight based on the total amount of the photosensitive resin composition.

The photosensitive resin composition of the present invention may further contain various curing agents which can promote thermal curing of the resin composition. Examples of the curing agent include a nitrogen-containing organic compound, a silicone resin curing agent, and Metal alkoxide, hydroxymethyl-containing melamine derivative or methylol group-containing urea derivative.

The photosensitive resin composition of the present invention preferably has a negative photosensitive property. By having a negative photosensitive property, coloring at the time of thermosetting is suppressed, and a cured film having higher transparency can be obtained. Further, since it has a negative photosensitive property, it is possible to obtain a cured film which is easy to carry out in the case of UV curing, and which is excellent in hardness, moist heat resistance, artificial sweat resistance, adhesion, chemical resistance, and vacuum resistance.

A description will be given of a production method representative of the photosensitive resin composition of the present invention. For example, a (F) decane compound is added to any (E) solvent and stirred. Next, (C) a photopolymerization initiator, (D) a metal chelate compound, (G) a maleimide compound, (H) a ruthenium compound, (I) a polyfunctional epoxy compound, and other additives are added and stirred. Let it dissolve. Further, (A) an acrylic resin, (B) a radically polymerizable compound, (B2) a radically polymerizable compound containing an anthracene skeleton, and (B3) a carboxyl group-containing radically polymerizable compound are added and stirred for 20 minutes to 3 minutes. It becomes a homogeneous solution in hours. Then, the resulting solution was filtered to obtain a photosensitive resin composition of the present invention.

A method of forming a cured film having a pattern by using the photosensitive resin composition of the present invention will be described by way of example.

First, the photosensitive resin composition of the present invention is applied onto a substrate. As the substrate, for example, a metal oxide such as ITO, a metal such as molybdenum, silver, copper or aluminum, or a CNT (Carbon Nano Tube) is formed on the glass as an electrode or a wiring substrate. Examples of the coating method include micro gravure coating, spin coating, dip coating, curtain coating, roll coating, and spraying. Apply and sew. The coating film thickness differs depending on the coating method, the solid content concentration or the viscosity of the photosensitive resin composition, and the like, but the film thickness after application and prebaking is usually 0.1 to 15 μm.

Next, the substrate coated with the photosensitive resin composition is prebaked to prepare a prebaking film of the photosensitive resin composition. The prebaking is carried out using an oven, a hot plate or an infrared ray, etc., preferably at 50 to 150 ° C for 30 seconds to several hours. If necessary, it may be prebaked at 80 ° C for 2 minutes, pre-baked at 120 ° C for 2 minutes, etc., and pre-baked in two or more stages.

After prebaking, exposure is performed using an exposure machine such as a stepper, a mirror projection mask aligner (MPA), or a parallel mask aligner (PLA). As the active chemical line to be irradiated during exposure, ultraviolet rays, visible rays, electron beams, X-rays, KrF (wavelength 248 nm) lasers or ArF (wavelength 193 nm) lasers or the like can be used, but it is preferable to use a j-line of a mercury lamp ( Wavelength 313 nm), i-line (wavelength 365 nm), h-line (wavelength 405 nm) or g-line (wavelength 436 nm). Further, the exposure amount is usually about 10 to 4000 J/m ² (the value of the i-ray illuminance meter), and the exposure can be performed through a mask having a desired pattern as needed.

Pre-development baking can also be carried out as needed. By performing pre-development baking, effects such as an increase in resolution during development and an increase in allowable range of development conditions can be expected. The baking temperature at this time is preferably 50 to 180 ° C, more preferably 60 to 150 ° C. The baking time is preferably from 10 seconds to several hours. If it is in the above range, the reaction proceeds well and can be completed with a short development time.

Then, by using an automatic developing device or the like, after exposure The film was developed for any time, and the unexposed portion was removed with a developing solution to obtain a relief pattern.

As the developer, a well-known alkaline developer is generally used. Examples of the developer include an organic alkaline developing solution or ammonia, tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and triethyl ethane. Amine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine or six An aqueous solution of a compound which exhibits basicity such as methylene diamine is preferably an aqueous solution of a compound which exhibits basicity, that is, an aqueous alkaline solution.

Further, as the developer, an alcohol, a ketone, an ether, N-methyl-2-pyrrolidone, or N-ethenyl group similar to the solvent (E) contained in the photosensitive resin composition may be used. 2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl hydrazine, hexamethylphosphonium triamine or γ-butyrolactone. Further, it is also possible to use such solvents with methanol, ethanol, isopropyl alcohol, water, methyl carbitol, ethyl carbitol, toluene, xylene, ethyl lactate, ethyl pyruvate, propylene glycol alone. Photosensitive properties such as methyl ether acetate, methyl-3-methoxypropionate, ethyl-3-ethoxypropionate, 2-heptanone, cyclopentanone, cyclohexanone or ethyl acetate A mixture of weak solvent combinations of resin compositions.

The development treatment can be carried out by directly applying the above-mentioned developing solution to the film after the exposure, and irradiating the above-mentioned developing solution into a mist, immersing the exposed film in the above developing solution, and exposing the film. The subsequent film is subjected to ultrasonic waves or the like while being immersed in the above-described developing solution. Further, it is preferred that the exposed film is brought into contact with the developer for 5 seconds to 10 minutes.

Preferably, after the development process, the relief pattern formed by the development is washed by the rinse liquid. As the rinsing liquid, when an alkaline aqueous solution is used as the developing solution, water is preferred. Further, an alcohol such as ethanol or isopropyl alcohol, an ester such as propylene glycol monomethyl ether acetate, or an acid such as carbon dioxide gas or hydrochloric acid or acetic acid may be added to the water to be rinsed.

When rinsing with an organic solvent, methanol, ethanol, isopropanol, ethyl lactate, ethyl pyruvate, propylene glycol monomethyl ether acetate, methyl-3-, which is highly compatible with the developer, is preferred. Methoxy propionate, ethyl-3-ethoxypropionate, 2-heptanone or ethyl acetate.

It can also be used for intermediate baking after development. By performing the intermediate baking, the resolution after the heat curing can be expected to be improved, and the effect of the pattern shape after the heat curing can be controlled. The intermediate baking is an oven, a hot plate or an infrared ray, etc., as a baking temperature, preferably 60 to 250 ° C, more preferably 70 to 220 ° C. The baking time is preferably from 10 seconds to several hours.

Next, the cured film of the photosensitive resin composition of the present invention is obtained by heating at a temperature of 120 to 280 ° C for 10 minutes to several hours. This heat treatment can be carried out under an air atmosphere or an inert gas atmosphere such as nitrogen. Further, the heat treatment may be carried out at a stepwise temperature or continuously, and may be carried out for 5 minutes to 5 hours. For example, a method of heat-treating each for 30 minutes at 130 ° C, 200 ° C, and 250 ° C, or a method of linearly raising the temperature for 2 hours from room temperature to 250 ° C may be mentioned.

The film thickness of the cured film obtained by thermally curing the photosensitive resin composition of the present invention is preferably 0.1 to 15 μm. Further, the film thickness is preferably 1.5 μm. The hardness is 4H or more and the transmittance is 90% or more. Furthermore, the transmittance as referred to herein means the transmittance at a wavelength of 400 nm. Hardness or transmittance can be adjusted by the choice of exposure amount and heat hardening temperature.

The cured film obtained by thermally curing the photosensitive resin composition of the present invention can be used for a protective film for a touch panel, various hard coating materials, a planarizing film for a TFT, an overcoat layer for a color filter, an antireflection film, or Each of the protective film such as a passivation film, an optical filter, an insulating film for a touch panel, an insulating film for a TFT, or the like, or a photo spacer for a color filter. Among these, from the viewpoint of high hardness, transparency, chemical resistance, vacuum resistance, and heat resistance, it can be suitably used as a protective film for a touch panel or an insulating film for a touch panel. Examples of the touch panel include a resistive film type, an optical type, an electromagnetic induction type, or an electrostatic capacity type. Among them, the cured film of the present invention is particularly suitable because the electrostatic capacitance type touch panel requires a particularly high hardness.

In addition, the cured film obtained by thermally curing the photosensitive resin composition of the present invention can be suitably used as a metal wiring protective film because of its high moist heat resistance and artificial sweat resistance. By forming the cured film of the present invention on the metal wiring, deterioration due to corrosion of the metal or the like (conductivity, reduction in resistance, and the like) can be prevented. The metal wiring to be protected includes, for example, a group selected from the group consisting of molybdenum, silver, copper, aluminum, chromium, titanium, ITO, IZO (Indium Zinc Oxide), AZO (Aluminum Zinc Oxide), ZnO _2, and CNT. More than one type of metal wiring. In addition, the cured film obtained by thermally curing the photosensitive resin composition of the present invention is suitably used as a protective film or insulation containing one or more kinds of metal wiring selected from the group consisting of molybdenum, silver, copper, aluminum, and CNT. membrane.

[Examples]

The present invention will be specifically described below by way of examples and comparative examples, but the present invention is not limited by the scope. Further, as for the abbreviations used in the compounds used, the names are shown below.

AcOH: Acetic acid

Al-A: aluminum chelate A (made by Chuanyan Precision Chemical Co., Ltd.; ginsengylacetate) aluminum (III)

BAPF: 9,9-bis[4-(3-propenyloxypropoxy)phenyl]indole

BDG: butyl diglycol, diethylene glycol mono-n-butyl ether

BGPP: 2,2-bis(4-glycidoxyphenyl)propane (manufactured by Tokyo Chemical Industry Co., Ltd.)

BMI-70: 3,3'-diethyl-5,5'-dimethyl-4,4'-bis(maleimide)diphenylmethane (manufactured by KI Chemical Co., Ltd.)

BMI-80: 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane (made by KI Chemical Co., Ltd.)

BPEF: 9,9-bis[4-(2-hydroxyethoxy)phenyl]anthracene (Osaka Gas Chemical Co., Ltd.)

BYK-333: Oxygenated surfactant (BYK Chemical Japan Co., Ltd.)

DPHA: KAYARAD (registered trademark) DPHA (manufactured by Nippon Kayaku Co., Ltd.; dipentaerythritol hexaacrylate)

EA-0250P: Ogsol (registered trademark) EA-0250P (Osaka Gas Chemical Co., Ltd.)

EDM: diethylene glycol ethyl methyl ether

EtOH: ethanol

HCl: hydrochloric acid

HNO ₃ : Nitric acid

H ₃ PO ₄ : phosphoric acid

IC-907: IRGACURE (registered trademark) 907 (manufactured by BASF; 2-methyl-1-[4-(methylthio)phenyl]-2- Polinidopropan-1-one)

ITO: indium tin oxide

KBM-1403: 4-styryltrimethoxydecane (Shin-Etsu Chemical Co., Ltd.)

KBM-403: 3-glycidoxypropyltrimethoxydecane (Shin-Etsu Chemical Co., Ltd.)

KBM-503: 3-methacryloxypropyltrimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd.)

KBM-5103: 3-propenyloxypropyltrimethoxydecane (Shin-Etsu Chemical Co., Ltd.)

KBM-803: 3-mercaptopropyltrimethoxydecane (Shin-Etsu Chemical Co., Ltd.)

KBM-903: 3-Aminopropyltrimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd.)

KBE-9007: 3-Isocyanatepropyltriethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd.)

KBE-9103: 3-triethoxydecyl-N-(1,3-dimethylbutylidene) propylamine (manufactured by Shin-Etsu Chemical Co., Ltd.)

KBM-9659: 1,3,5-gin(3-trimethoxydecylpropyl)iso-cyanuric acid (Shin-Etsu Chemical Co., Ltd.)

MAM: Mo/Al/Mo (molybdenum/aluminum/molybdenum)

MB: 3-methoxy-1-butanol

MEA: monoethanolamine, 2-aminoethanol

M-510: Aronix (registered trademark) M-520 (East Asia Synthetic Co., Ltd.)

M-520: Aronix (registered trademark) M-510 (East Asia Synthetic Co., Ltd.)

NaCl: sodium chloride

Na ₂ HPO ₄ : disodium hydrogen phosphate

NaOH: sodium hydroxide

N-300: Repellent stripping solution (manufactured by Nagase Chemtex; MEA/BDG=30/70)

OFPR-800: Positive photoresist (Tokyo Chemical Industry Co., Ltd.)

OXE-01: IRGACURE (registered trademark) OXE-01 (manufactured by BASF; 1-[4-(phenylthio)phenyl]oct-1,2-dione-2-(O-benzylidene) fluorene)

PCT: Pressure cooking test

PGMEA: propylene glycol monomethyl ether acetate

PG-100: Ogsol (registered trademark) PG-100 (Osaka Gas Chemical Co., Ltd.)

TC-401: Orgatix (registered trademark) TC-401 (Matsumoto Precision Chemical Co., Ltd.; 肆 (acetamidone) titanium (IV))

TMAH: tetramethylammonium hydroxide

TMPU: 1-(3-trimethoxydecylpropyl)urea

VG-3101L: TECHMORE (registered trademark) VG-3101L (PRINTEC (share) system; 1,1-bis(4-epoxypropoxyphenyl)-1-[4-[1-(4-epoxypropyl) Oxyphenyl)-1-methylethyl]phenyl]ethane)

X-12-967YP: 2-(3-trimethoxydecylpropyl)-4-(N-t-butyl)amino-4-oxobutanoic acid (manufactured by Shin-Etsu Chemical Co., Ltd.)

ZC-150: Orgatix (registered trademark) ZC-150 (Matsumoto Precision Chemical Co., Ltd.; bismuth (ethyl acetonide) zirconium (IV))

Nacem Mg: Nacem (registered trademark) Magnesium (manufactured by Nippon Chemical Industry Co., Ltd.; bis(ethylmercaptoacetate) magnesium (II))

Synthesis Example 1 Synthesis of Acrylic Resin Solution (A-1)

0.821 g (1 mol%) of 2,2'-azobis(isobutyronitrile) and 29.09 g of PGMEA were placed in the flask, and the mixture was sufficiently purged with nitrogen by bubbling in a flask, and then the temperature was raised to 80 °C. Then, a mixed solution of 26.88 g (30 mol%) of N-cyclohexylmaleimine, 19.37 g (45 mol%) of methacrylic acid, and 12.52 g (25 mol%) of methyl methacrylate was added over 4 hours at 80 ° C. Stir under heating for 6 hours. Next, 14.22 g (20 mol%) of glycidyl methacrylate, 0.676 g (1 mol%) of dimethylbenzylamine, and 0.186 g (0.3 mol%) of 4-methoxyphenol were added to the obtained solution. 59.06 g of PGMEA was heated and stirred at 70 ° C for 2 hours to obtain an acrylic resin solution (A-1). PGMEA was added to the obtained acrylic resin solution (A-1) so that the solid content concentration might become 35 weight%. The acrylic resin had a weight average molecular weight (Mw) of 11,000, an acid value of 100, and a double bond equivalent of 730.

Synthesis Example 2 Synthesis of Acrylic Resin Solution (A-2)

0.821 g (1 mol%) of 2,2'-azobis(isobutyronitrile), 26.15 g of PGMEA, 13.44 g (15 mol%) of N-cyclohexylmaleimide, 19.37 g (45 mol%) of methacrylic acid were used. 20.02 g (40 mol%) of methyl methacrylate, 14.22 g (20 mol%) of glycidyl methacrylate, 0.676 g (1 mol%) of dimethylbenzylamine, 0.186 g (0.3 mol%) of 4-methyl Epoxyphenol and 53.10 g of PGMEA were polymerized in the same manner as in Synthesis Example 1 to obtain an acrylic resin solution (A-2). PGMEA was added to the obtained acrylic resin solution (A-2) so that the solid content concentration might become 35 weight%. The acrylic resin has a weight average molecular weight (Mw) of 15,000, an acid value of 109, and a double bond equivalent of 670.

Synthesis Example 3 Synthesis of Acrylic Resin Solution (A-3)

0.821 g (1 mol%) of 2,2'-azobis(isobutyronitrile), 25.17 g of PGMEA, 8.96 g (10 mol%) of N-cyclohexylmaleimide, 19.37 g (45 mol%) of methacrylic acid were used. 22.53 g (45 mol%) methyl methacrylate, 14.22 g (20 mol%) glycidyl methacrylate, 0.676 g (1 mol%) dimethylbenzylamine, 0.186 g (0.3 mol%) 4-methyl Epoxyphenol and 51.11 g of PGMEA were polymerized in the same manner as in Synthesis Example 1 to obtain an acrylic resin solution (A-3). In the obtained acrylic resin solution (A-3), PGMEA was added to have a solid content concentration of, for example, 35% by weight. The acrylic resin had a weight average molecular weight (Mw) of 17,000, an acid value of 108, and a double bond equivalent of 650.

Synthesis Example 4 Synthesis of Acrylic Resin Solution (A-4)

0.821 g (1 mol%) of 2,2'-azobis(isobutyronitrile), 33.01 g of PGMEA, 44.81 g (50 mol%) of N-cyclohexylmaleimide, 19.37 g (45 mol%) of methacrylic acid were used. 2.50 g (5 mol%) of methyl methacrylate, 14.22 g (20 mol%) of glycidyl methacrylate, 0.676 g (1 mol%) of dimethylbenzylamine, 0.186 g (0.3 mol%) of 4-methyl Epoxyphenol and 67.01 g of PGMEA were polymerized in the same manner as in Synthesis Example 1 to obtain an acrylic resin solution (A-4). In the obtained acrylic resin solution (A-4), PGMEA was added to have a solid content concentration of, for example, 35% by weight. The acrylic resin had a weight average molecular weight (Mw) of 11,000, an acid value of 104, and a double bond equivalent of 810.

Synthesis Example 5 Synthesis of Acrylic Resin Solution (A-5)

0.821 g (1 mol%) of 2,2'-azobis(isobutyronitrile), 35.14 g of PGMEA, 53.77 g (60 mol%) of N-cyclohexylmaleimide, 17.22 g (40 mol%) of methacrylic acid were used. 10.66g (15mol%) methacrylic acid epoxy Propyl ester, 0.676 g (1 mol%) of dimethylbenzylamine, 0.186 g (0.3 mol%) of 4-methoxyphenol, and 71.34 g of PGMEA were polymerized in the same manner as in Synthesis Example 1 to obtain an acrylic resin solution (A- 5). PGMEA was added to the obtained acrylic resin solution (A-5) so that the solid content concentration might be 35 weight%. The acrylic resin had a weight average molecular weight (Mw) of 12,000, an acid value of 86, and a double bond equivalent of 1090.

Synthesis Example 6 Synthesis of Acrylic Resin Solution (A-6)

0.821 g (1 mol%) of 2,2'-azobis(isobutyronitrile), 28.35 g of PGMEA, 25.38 g (30 mol%) of N-phenylmaleimide, 19.37 g (45 mol%) of methacrylic acid were used. 12.52 g (25 mol%) methyl methacrylate, 14.22 g (20 mol%) glycidyl methacrylate, 0.676 g (1 mol%) dimethylbenzylamine, 0.186 g (0.3 mol%) 4-methyl Epoxyphenol and 57.55 g of PGMEA were polymerized in the same manner as in Synthesis Example 1 to obtain an acrylic resin solution (A-6). PGMEA was added to the obtained acrylic resin solution (A-6) so that the solid content concentration might become 35 weight%. The acrylic resin had a weight average molecular weight (Mw) of 12,000, an acid value of 105, and a double bond equivalent of 710.

Synthesis Example 7 Synthesis of Acrylic Resin Solution (A-7)

0.821 g (1 mol%) of 2,2'-azobis(isobutyronitrile), 29.39 g of PGMEA, 27.49 g (30 mol%) of N-benzylmaleimide, 19.37 g (45 mol%) of methacrylic acid were used. 12.52 g (25 mol%) methyl methacrylate, 14.22 g (20 mol%) glycidyl methacrylate, 0.676 g (1 mol%) dimethylbenzylamine, 0.186 g (0.3 mol%) 4-methyl Acetylphenol and 59.67 g of PGMEA were polymerized in the same manner as in Synthesis Example 1 to obtain an acrylic resin solution (A-7). PGMEA was added to the obtained acrylic resin solution (A-7) so that the solid content concentration might become 35 weight%. Acrylic resin weight The average molecular weight (Mw) was 11,000, the acid value was 98, and the double bond equivalent was 740.

Synthesis Example 8 Synthesis of Acrylic Resin Solution (A-8)

0.821 g (1 mol%) of 2,2'-azobis(isobutyronitrile), 25.97 g of PGMEA, 20.58 g (30 mol%) of N-(2-hydroxyethyl)maleimide, 19.37 g (45 mol) was used. %) methacrylic acid, 12.52 g (25 mol%) methyl methacrylate, 14.22 g (20 mol%) glycidyl methacrylate, 0.676 g (1 mol%) dimethylbenzylamine, 0.186 g (0.3 mol %) 4-methoxyphenol and 52.72 g of PGMEA were polymerized in the same manner as in Synthesis Example 1 to obtain an acrylic resin solution (A-8). PGMEA was added to the obtained acrylic resin solution (A-8) so that the solid content concentration might become 35 weight%. The acrylic resin had a weight average molecular weight (Mw) of 13,000, an acid value of 103, and a double bond equivalent of 670.

Synthesis Example 9 Synthesis of Acrylic Resin Solution (A-9)

0.821 g (1 mol%) of 2,2'-azobis(isobutyronitrile), 29.24 g of PGMEA, 26.88 g (30 mol%) of N-cyclohexylmaleimide, 19.37 g (45 mol%) of methacrylic acid were used. 5.01 g (10 mol%) of methyl methacrylate, 7.81 g (15 mol%) of styrene, 14.22 g (20 mol%) of glycidyl methacrylate, 0.676 g (1 mol%) of dimethylbenzylamine, 0.186 g (0.3 mol%) 4-methoxyphenol and 59.37 g of PGMEA were polymerized in the same manner as in Synthesis Example 1 to obtain an acrylic resin solution (A-9). To the obtained acrylic resin solution (A-9), PGMEA was added so that the solid content concentration became, for example, 35% by weight. The acrylic resin had a weight average molecular weight (Mw) of 11,000, an acid value of 105, and a double bond equivalent of 730.

Synthesis Example 10 Synthesis of Acrylic Resin Solution (A-10)

0.821 g (1 mol%) of 2,2'-azobis(isobutyronitrile) and 34.64 g of PGMEA were added to the flask. Next, 26.43 g (30 mol%) of benzyl methacrylate, 21.52 g (50 mol%) of methacrylic acid, and 22.03 g (20 mol%) of tricyclo[5.2.1.0 ^2,6 ]non-8-ester of methacrylic acid were added. After stirring at room temperature for a while, the mixture was sufficiently nitrogen-substituted by bubbling in a flask, and then heated and stirred at 70 ° C for 5 hours. Next, 14.22 g (20 mol%) of glycidyl methacrylate, 0.676 g (1 mol%) of dimethylbenzylamine, and 0.186 g (0.3 mol%) of 4-methoxyphenol were added to the obtained solution. 70.33 g of PGMEA was heated and stirred at 90 ° C for 4 hours to obtain an acrylic resin solution (A-10). PGMEA was added to the obtained acrylic resin solution (A-10) so that the solid content concentration might be 35 weight%. The acrylic resin had a weight average molecular weight (Mw) of 30,000, an acid value of 117, and a double bond equivalent of 840.

Synthesis Example 11 Synthesis of Acrylic Resin Solution (A-11)

0.821 g (1 mol%) of 2,2'-azobis(isobutyronitrile), 29.29 g of PGMEA, 21.52 g (50 mol%) of methacrylic acid, 22.03 g (20 mol%) of trimethyl methacrylate [5.2.1.0] was used. ^2,6 ]癸-8-ester, 15.62 g (30 mol%) of styrene, 14.22 g (20 mol%) of glycidyl methacrylate, 0.676 g (1 mol%) of dimethylbenzylamine, 0.186 g (0.3 Mol%) 4-methoxyphenol and 59.47 g of PGMEA were polymerized in the same manner as in Synthesis Example 10 to obtain an acrylic resin solution (A-11). In the obtained acrylic resin solution (A-11), PGMEA was added to have a solid content concentration of, for example, 35% by weight. The acrylic resin had a weight average molecular weight (Mw) of 15,000, an acid value of 109, and a double bond equivalent of 730.

Synthesis Example 12 Synthesis of Acrylic Resin Solution (A-12)

0.821 g (1 mol%) of 2,2'-azobis(isobutyronitrile), 23.34 g of PGMEA, 21.52 g (50 mol%) of methacrylic acid, and 10.01 g (20 mol%) were used. Methyl methacrylate, 15.62 g (30 mol%) styrene, 14.22 g (20 mol%) glycidyl methacrylate, 0.676 g (1 mol%) dimethylbenzylamine, 0.186 g (0.3 mol%) 4 -Methoxy phenol and 47.39 g of PGMEA were polymerized in the same manner as in Synthesis Example 10 to obtain an acrylic resin solution (A-12). PGMEA was added to the obtained acrylic resin solution (A-12) so that the solid content concentration might become 35 weight%. The acrylic resin had a weight average molecular weight (Mw) of 20,000, an acid value of 113, and a double bond equivalent of 610.

The compositions of Synthesis Examples 1 to 12 are collectively shown in Table 1.

The evaluation method in Example 1 is shown below.

(1) Solid content concentration of acrylic resin solution

In an aluminum cup having a measured weight, 1 g of an acrylic resin solution was weighed and heated at 250 ° C for 30 minutes using a hot plate (HP-1SA; manufactured by AS ONE Co., Ltd.), and evaporated to dryness. After heating, the weight of the aluminum cup in which the solid component remained was measured, and the weight of the residual solid component was calculated from the phase difference portion before and after the heating, and the solid content concentration of the acrylic resin solution was determined.

(2) Weight average molecular weight (Mw) of acrylic resin

A GPC analyzer (HLC-8220; manufactured by Tosoh Corporation) was used, and THF was used as a fluidized layer to carry out GPC measurement, which was obtained by polystyrene conversion.

(3) Acid price

A potentiometric auto-titration device (AT-510; manufactured by Kyoto Electronics Industry Co., Ltd.) was used, and a 0.1 mol/L NaOH/EtOH solution was used as a titration reagent, and was subjected to potentiometric titration according to "JIS K2501 (2003)". Determination of acid value.

(4) Double bond equivalent

According to "JIS K0070 (1992)", the iodine value of the resin was measured and calculated.

(5) Pre-processing of the substrate

A glass substrate in which three layers of Mo/Al/Mo are formed by sputtering using a desktop type surface finishing apparatus (PL16-110; SEN special light source (manufactured by SEN)) (Sanrong Vacuum Industry Co., Ltd.) The following is a "MAM substrate"), a glass substrate on which ITO is formed by sputtering (manufactured by Sanyo Vacuum Industries Co., Ltd.; hereinafter referred to as "ITO substrate"), and after UV-O ₃ cleaning for 100 seconds, The ultrapure water was washed, and the water droplets on the surface were blown off with an air lance of compressed air, and heated at 130 ° C for 3 minutes using a hot plate, and subjected to dehydration baking treatment. TEMPAX glass substrate (manufactured by AGC Techno Glass Co., Ltd.) and a glass substrate (single-layer Cr film-forming substrate; manufactured by Kurt Seiya Co., Ltd.; "Cr substrate"); Use before pre-processing.

(6) Sensitivity

The developed film of the photosensitive resin composition was produced on the Cr substrate by the method described in the following Example 1. After development, an FPD inspection microscope (MX-61L; manufactured by OLYMPUS Co., Ltd.) was used to observe the resolution pattern, and the 30 μm L&S pattern was formed to have an exposure amount of 1 to 1 (the value of the i-ray illuminance meter, the following is "Optimum exposure" is used as sensitivity.

(7) Resolution

A cured film of a photosensitive resin composition was produced on the Cr substrate by the method described in the following Example 1. The FPD inspection microscope was used to observe the resolution pattern of the produced cured film, and the minimum pattern size among the optimum exposure amounts was taken as the resolution.

(8) Transmission rate

A cured film of a photosensitive resin composition was produced on the TEMPAX glass substrate by the method described in the following Example 1. Using an ultraviolet-visible spectrophotometer (MultiSpec-1500; manufactured by Shimadzu Corporation), only the TEMPAX glass substrate was first measured, and its ultraviolet-visible absorption spectrum was used as a reference. Next, the cured film produced was measured by a single beam, and the transmittance per 1.5 μm at a wavelength of 400 nm was determined, and the transmittance was calculated from the difference from the standard.

(9) pencil hardness

A cured film of a photosensitive resin composition was produced on the Cr substrate by the method described in the following Example 1. The pencil hardness of the produced cured film was measured by a manual pencil scratch hardness tester (850-56; manufactured by Coating Tester Co., Ltd.) in accordance with "JIS K5600-5-4 (1999)".

(10) Chemical resistance

A cured film of a photosensitive resin composition was produced on the ITO substrate by the method described in the following Example 1. The prepared cured film was immersed in an acid liquid (weight ratio: HCl/HNO ₃ /H ₂ O=50/7.5/42.5) heated to 40 ° C for 240 seconds, and rinsed with water for 2 minutes.

Next, the adhesion between the cured film and the substrate was measured in accordance with "JIS K5600-5-6 (1999)". Specific measurement methods are described below. Using a utility knife to draw a parallel line of 11 vertical × 11 horizontal lines perpendicular to the cured film at a distance of 1 mm from the surface of the self-cured film on the ITO substrate to the surface of the ITO, 100 squares of 1 mm × 1 mm were produced. grid. Next, on the surface of the cured film having a square, attached to Cellotape (registered trademark) (No. 405 (industrial); NICHIBAN (stock); width = 18 mm, thickness = 0.050 mm, adhesion = 3.93 N / 10 mm, tensile strength = 41.6 N/10 mm), and rubbed with an eraser ("JIS S6050 (2008)") to adhere them, and one end of the tape was grasped, and the ITO substrate was held at right angles to be peeled off instantaneously. After peeling, the number of peeling of the squares was evaluated by visual observation. According to the peeling area of the square, as judged below, 3B or more is regarded as qualified.

5B: peeling area = 0%

4B: Peeling area <5%

3B: Peeling area = 5~14%

2B: peeling area = 15~34%

1B: Peeling area = 35~64%

0B: peeling area = 65~100%

(11) Vacuum resistance

A cured film of a photosensitive resin composition was produced on the ITO substrate by the method described in the following Example 1. The prepared cured film was subjected to a sputtering apparatus (HSR-521A; manufactured by Shimadzu Corporation) and depressurized to a pressure of 7.0 to 7.5 × 10 ^-4 while being heated to 100 ° C, and exposed to a high vacuum. . Then, using a desktop ultrasonic cleaning machine (UT-104; manufactured by SHARP), the cured film exposed to high vacuum was immersed in water at 40 ° C while irradiating ultrasonic waves of 39 kHz and 100 W. minute.

Then, in the same manner as in the above (10), the adhesion between the cured film and the substrate was measured in accordance with "JIS K5600-5-6 (1999)".

(12) Heat and humidity resistance

A cured film of a photosensitive resin composition was produced on the MAM substrate by the method described in the following Example 1. The cured film produced was subjected to PCT (temperature = 121 ° C, humidity = 100% RH, gas pressure = 2 atm) using a highly accelerated life measuring device (Hast Chamber EHS-221MD), and left for 20 hours. After 20 hours from PCT, the area on which the MAM surface on the MAM substrate was discolored to black and the appearance of the surface of the cured film were visually evaluated. According to the change in the color change area of the surface of the MAM and the appearance of the surface of the cured film, it was judged as follows, and A+, A, and B were regarded as qualified.

A+: The discoloration area of the surface of MAM is 0%, and there is no change in the appearance of the surface of the cured film.

A: The discoloration area of the surface of MAM is <5%, and the appearance of the surface of the cured film is not changed. Chemical

B: The discoloration area of the surface of MAM is 5~14%, and the appearance of the surface of the cured film is not changed.

C: The discoloration area of the surface of MAM is 15~34%, and the appearance of the surface of the cured film is not changed.

D: The discoloration area of the surface of MAM is 35~64%, and the appearance of the surface of the cured film is not changed.

E: The color change area of the surface of MAM is 65~100%, and the appearance of the surface of the cured film is not changed.

F: The discoloration area of the surface of the MAM is 65 to 100%, the surface of the cured film is cracked, or the cured film is peeled off from the substrate.

(13) Artificial sweat resistance

A cured film of a photosensitive resin composition was produced on the MAM substrate by the method described in the following Example 1. Produced in the hardened film, dropping the artificial sweat solution (NaCl = 1g, L- lactic acid = 0.1g, Na ₂ HPO ₄ .12 0.25 g hydrate =, L-histamine acid hydrochloride. Monohydrate = 0.025 g, a mixed solution of H ₂ O = 100 g) was made to have a diameter of 5 mm, and placed at 23 ° C to be dried. After drying, it was allowed to stand for 25 days (600 hours) under the conditions of temperature = 60 ° C and humidity = 90% RH using a constant temperature and humidity tester (thermostat PH-2ST). After 35 days, the area of the MAM surface corrosion and the presence or absence of the appearance of the cured film surface were visually evaluated for the portion of the MAM substrate where the artificial sweat solution was dropped. According to the corrosion area of the surface of the MAM and the appearance change of the surface of the cured film, it is judged as follows, and A+, A, and B are regarded as qualified.

A+: Corrosion area of MAM surface = 0%, appearance change without hardened film surface

A: The corrosion area of the surface of MAM is <5%, and there is discoloration on the surface of the cured film.

B: The corrosion area of the surface of MAM is 5~14%, and there is discoloration on the surface of the cured film.

C: The corrosion area of the surface of MAM is 15~34%, and there is discoloration on the surface of the cured film.

D: The corrosion area of the surface of MAM is 35~64%, and there is discoloration on the surface of the cured film.

E: The corrosion area of the surface of MAM is 65~100%, and there is discoloration on the surface of the cured film.

F: The corrosion area of the surface of the MAM is 65 to 100%, the surface of the cured film is cracked, or the cured film is peeled off from the substrate.

(14) Adhesion and storage stability of MAM substrates

A cured film of a photosensitive resin composition was produced on the MAM substrate by the method described in the following Example 1. The cured film produced was measured for the adhesion to the substrate by a method similar to the above (10) in accordance with "JIS K5600-5-6 (1999)".

A part of the photosensitive resin composition prepared by the method described in the following Example 1 was placed at 23 ° C for 7 days. After the lapse of the next day, a cured film of the photosensitive resin composition placed on the MAM substrate for 7 days at 23 ° C was produced by the method described in the following Example 1. With respect to the cured film produced, the adhesion to the substrate of the cured film was measured in the same manner as in the above (10) in accordance with "JIS K5600-5-6 (1999)".

Example 1

Under a yellow light, weigh 1.282 g PGMEA, 6.375 g MB, 8.500 g EDM, and add 0.0693 g KBM-903 and stir. Next, 0.173 g of OXE-01, 0.0347 g of ZC-150, and 0.150 g of BYK-333 in a 5% by weight solution of PGMEA were added and stirred to dissolve. Next, 4.950 g of the acrylic resin solution (A-1) obtained in Synthesis Example 1 (35 wt% of PGMEA solution) was added. ), 3.465 g of a 50% by weight solution of DPHA in DPHA was stirred to form a homogeneous solution. Then, the resulting solution was filtered through a 0.2 μm filter to prepare a negative photosensitive resin composition 1.

Using a spin coater (MS-A100; manufactured by MIKASA Co., Ltd.), the prepared photosensitive resin composition 1 was applied by spin coating at an arbitrary number of revolutions, and then a hot plate (SCW-636) was used. , manufactured by Dainippon SCREEN Co., Ltd., prebaked at 100 ° C for 3 minutes to prepare a prebaked film having a film thickness of about 2.0 μm.

The double-precision single-sided exposure apparatus (mask aligner PEM-6M; UNION optical system) was used to make the pre-baked film with a gray scale mask for sensitivity measurement (MDRM MODEL 4000). -5-FS; manufactured by Opto-Line International), patterned exposure of j-line (wavelength 313 nm), i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g-line (wavelength 436 nm) of an ultrahigh pressure mercury lamp. After the exposure, a small developing device (AD-2000; manufactured by Takizawa Seiki Co., Ltd.) using lithography was used for development for 90 seconds in a 2.38 wt% TMAH aqueous solution, and rinsed with water for 30 seconds. After the development, an inert oven "DN43HI" (trade name, manufactured by YAMATO Scientific Co., Ltd.) was used, and the film was thermally cured at 230 ° C for 1 hour in a nitrogen atmosphere to prepare a cured film having a film thickness of about 1.5 μm.

Examples 2 to 49 and Comparative Examples 1 to 6

In the same manner as the photosensitive resin composition 1, the photosensitive resin compositions 2 to 55 were prepared in the compositions described in Tables 2 to 6. The photosensitive characteristics and the characteristics of the cured film were evaluated in the same manner as in Example 1 using each of the obtained photosensitive resin compositions. The results are summarized in Tables 7-11.

Example 50

The touch panel member is fabricated in accordance with the following procedure.

(1) Production of ITO

ITO having a film thickness of 150 nm and a surface resistance of 15 Ω/□ was sputtered on a glass substrate having a thickness of about 1 mm by sputtering at an RF power of 1.4 kW and a vacuum of 6.65 × 10 ^-1 Pa for 12.5 minutes. Film formation. Next, a positive-type photoresist OFPR-800 was applied onto the ITO by spin coating using an arbitrary number of rotations, and then pre-baked at 80 ° C for 20 minutes using a hot plate to obtain a film thickness of 1.1 μm. Resistive film. Using a double-sided alignment single-sided exposure device, the resist film formed is separated by a mask, and the j-line (wavelength 313 nm), i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g of the ultrahigh pressure mercury lamp are used. The pattern (wavelength: 436 nm) was subjected to pattern exposure, and developed by a small developing device using lithography in a 2.38 wt% TMAH aqueous solution for 90 seconds and rinsed with water for 30 seconds. Next, ITO was immersed in an ITO etching solution (weight ratio: HCl/HNO ₃ /H ₂ O = 18/4.5/77.5) heated at 40 ° C for 80 seconds, and ITO was etched and rinsed with water for 2 minutes. Next, the resist stripping liquid N-300 (weight ratio: MEA/BDG=30/70) heated at 50 ° C was immersed for 2 minutes to remove the resist film, and patterned ITO having a film thickness of 150 nm was prepared. The glass substrate (corresponding to a in Fig. 1) of the symbol 2) in Fig. 1 and Fig. 2 .

(2) Production of transparent insulating film

Using the photosensitive resin composition 1 on the glass substrate produced in (1), a transparent insulating film of the photosensitive resin composition was produced by the method described in the above Example 1 (symbols of FIGS. 1 and 2) 3) (equivalent to b in Figure 1).

(3) Production of MAM wiring

On the glass substrate prepared in (2), molybdenum and aluminum were used as targets, and an acid solution was used (weight ratio: H ₃ PO ₄ /HNO ₃ /AcOH/H ₂ O=65/3/5/27) As the MAM etching solution, MAM wiring (symbol 4 in Figs. 1 and 2) was produced in the same manner as in (1) (corresponding to c in Fig. 1).

(4) Production of transparent protective film

On the glass substrate produced in (3), a photosensitive resin composition 1 was used, and a transparent protective film of a photosensitive resin composition was produced by the method described in the above Example 1. Using a digital multimeter (CDM-09N; manufactured by CUSTOM Co., Ltd.), after the conduction test of the connection portion was performed, the conduction of the current was confirmed (corresponding to Fig. 2).

[Industrial availability]

The cured film obtained by thermally curing the photosensitive resin composition of the present invention is suitable for various hard coat films such as a protective film of a touch panel, and other insulating films for touch sensors, liquid crystal or organic EL displays. A flattening film for a TFT, a metal wiring protective film, an insulating film, an antireflection film, an antireflection film, an optical filter, a cover layer for a color filter, a pillar, and the like.

a‧‧‧Top surface after transparent electrode formation

b‧‧‧Top surface after the formation of the insulating film

c‧‧‧Top surface diagram after metal wiring is formed

1‧‧‧ glass substrate

2‧‧‧Transparent electrode

3‧‧‧Transparent insulating film

4‧‧‧Wiring electrode

Claims (15)

A photosensitive resin composition containing (A) an acrylic resin, (B) a radically polymerizable compound, (C) a photopolymerization initiator, (D) a metal chelate compound, and (E) a solvent photosensitive resin a composition, wherein the (A) acrylic resin has a structure derived from maleimide represented by the general formula (1); (X represents a direct bond, an alkyl chain having a carbon number of 1 to 10, a stretched alkyl chain having a carbon number of 4 to 10, or an extended aryl chain having a carbon number of 6 to 15, and R ¹ represents hydrogen and a carbon number of 1~ 10 alkyl, 4 to 10 cycloalkyl, 2 to 7 alkenyl, 6 to 15 aryl, 1 to 6 alkoxy, 2 to 7 carbon An oxy group, an ester group having 2 to 7 carbon atoms, a hydroxyl group, a carboxyl group, an amine group or a nitro group). The photosensitive resin composition of claim 1, wherein the (D) metal chelate compound is one or more selected from the group consisting of a titanium chelate compound, a zirconium chelate compound, an aluminum chelate compound, and a magnesium chelate compound. Metal chelate compound. The photosensitive resin composition of claim 2, wherein the (D) metal chelate compound is a metal chelate compound represented by the formula (2); (M represents titanium, zirconium, aluminum or magnesium, and R ² represents hydrogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms, and R ³ and R ⁴ respectively Independently represents hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a hydroxyl group, and n is 0 to 4 The integer). The photosensitive resin composition of claim 3, wherein M is zirconium in the formula (2). The photosensitive resin composition according to any one of claims 1 to 4, further comprising (F) having a member selected from the group consisting of an amine group, a mercaptoamine group, a urea group, a ketimine group, an isocyanate group, a mercapto group, and a heterotrimer. a decane compound of a substituent in the group of a cyanate ring skeleton, a (meth)acrylic group, and a styryl group. The photosensitive resin composition according to any one of claims 1 to 5, which further contains (G) a maleimide compound. The photosensitive resin composition according to any one of claims 1 to 6, wherein the (B) radically polymerizable compound contains (B2) a radically polymerizable compound having an anthracene skeleton. The photosensitive resin composition according to any one of claims 1 to 7, wherein the (B) radically polymerizable compound contains (B3) a radical polymerization having a carboxyl group Sex compounds. The photosensitive resin composition according to any one of claims 1 to 8, which further contains (H) an anthracene compound. The photosensitive resin composition according to any one of claims 1 to 9, which further contains (I) a polyfunctional epoxy compound. A protective film or an insulating film of a metal wiring which is obtained by thermally curing a photosensitive resin composition according to any one of claims 1 to 10. A protective film or an insulating film of the metal wiring of claim 11, wherein the photosensitive resin composition is negative. A protective film or an insulating film of a metal wiring according to claim 11 or 12, wherein the metal wiring comprises one or more metal wirings selected from the group consisting of molybdenum, silver, copper, aluminum, and CNT. A touch panel comprising a protective film or an insulating film of a metal wiring according to any one of claims 11 to 13. A method of producing a touch panel, which is a protective film or an insulating film of a metal wiring obtained by thermally curing a photosensitive resin composition according to any one of claims 1 to 10.